Nonlinear optical materials containing polar disulfone-functionalized molecules

ABSTRACT

Nonlinear optical (NLO) compositions are disclosed which contain polar disulfone-functionalized molecules (PDFMs) incorporated in a polymeric material. When aligned noncentrosymmetrically in the polymeric material, the PDFMs generate a second-order NLO response. There is also disclosed: a method of preparing a NLO composition; novel PDFMs and novel polymers; and a new process for preparing PDFMs.

FIELD OF THE INVENTION

This invention pertains to (i) a nonlinear-optical (NLO) compositionthat contains a polymeric composition having polardisulfone-functionalized molecules (PDFMs) incorporated therein, (ii) aprocess for preparing a nonlinear-optical composition, (iii) a method ofgenerating a NLO response, (iv) novel PDFMs, (v) novel polymers, and(vi) a new method of preparing PDFMs.

BACKGROUND OF THE INVENTION

Organic NLO compositions have been developed to influence the direction,frequency, amplitude, and phase of light. Typical organic NLOcompositions contain a polymeric composition having polar NLO moleculesincorporated therein. Typical polar NLO molecules have electron donorand acceptor groups linked by conjugated π-electron systems. When lightis passed through the NLO compositions, the incorporated polar moleculesgenerate a NLO response. Polar NLO molecules have been incorporated intopolymeric compositions using one of two distinct methods.

In a first method, the polar NLO molecules are dissolved in a polymericcomposition. The polar NLO molecules are referred to as "guests", andthe polymeric composition is referred to as a "host". In such"guest-host" compositions, the NLO guest molecules are dispersed in thepolymeric host without being bonded thereto to form a polymeric NLOcomposition. Guest-host polymeric NLO compositions are disclosed, forexample, in EP-A-0,218,938 and U.S. Pat. No. 4,707,303.

In a second method, the polar NLO molecules are incorporated into apolymeric composition by covalently attaching the former to a polymer.An example of a polymer having NLO groups covalently bonded thereto isdisclosed in U.S. Pat. No. 5,006,729.

Whether polar NLO molecules are incorporated into a polymericcomposition by dispersing or bonding, the molecules need to be alignedto achieve a NLO response. It is known that NLO compositions can displaya second-order response when the χ.sup.(2) (chi squared)optically-responsive molecules are aligned noncentrosymmetrically.Noncentrosymmetric means that inversion symmetry is not present in thecomposition. Noncentrosymmetric molecular alignment has beenaccomplished by heating the polymeric composition to its glasstransition temperature (T_(g)), applying a DC electric field across thepolymeric composition to cause the incorporated NLO molecules to line upin the direction of the applied field (referred to as "poling"), andcooling the polymeric composition below T_(g) while the electric fieldis still being applied.

The following publications provide general background information on NLOmaterials: R. Dagani, "Chemists Crucial to Progress in Nonlinear OpticalMaterials", Chem. & Eng News 21-25 (Jun. 11, 1990); S. Tripathy et al.,"Nonlinear Optics and Organic Materials", Chemtech 747-752 (December1989); and D. S. Chemla and J. Zyss, "Nonlinear Optical Properties ofOrganic Molecules and Crystals", vols. I & II,, ch II-7 and II-8Academic Press, N.Y. (1987).

U.S. Pat. Nos. 3,932,526, 3,933,914, 3,984,357, 4,018,810, 4,069,233,4,156,696, and 4,357,405 disclose PDFMs and processes for preparingthose PDFMs. The PDFMs are disclosed to be useful as catalysts, dyes,and sensitizers. These patents do not teach or suggest that PDFMs willprovide second-order NLO effects when aligned noncentrosymmetrically ina polymeric composition.

I. I. Malentina et al., Inst. Org. Chem., Acad. Sci. Ukrainian SSR,Plenum Publishing (1980) (translated from Zhurnal Organicheskoi Khimii,v. 15, n. 11, pp. 2416-17 (November 1979)) discloses preparing adisulfonyl fluoride, p-(CH₃)₂ NC₆ H₄ CH═C(SO₂ F)₂, from methanedisulfonyl fluoride and 4-dimethylaminobenzaldehyde. No utility for thedisulfonyl fluoride is disclosed.

U.S. Pat. No. 4,973,429 discloses organic compositions having NLOproperties. The organic compositions are in the form of a film andcontain compounds of the formula: ##STR1## where X is ═CH-- or ═N--, R¹is C₁₂ -C₃₀ -alkyl, R² is hydrogen or C₁ -C₃₀ -alkyl, R³ is --NO₂, --CN,--CF₃, --COCF₃, --SO₂ CH₃ or --SO₂ CF₃, R⁴ is hydrogen or is defined inthe same way as R³, R⁵ , hydrogen or --NR⁶ R⁷ and R⁶ and R⁷independently of one another are hydrogen or C₁ -C₃₀ -alkyl, it alsobeing possible for any of the alkyl radicals to be partially fluorinatedor perfluorinated.

U.S. Pat. No. 5,006,729 discloses a NLO compound comprising an electrondonor group linked to an electron acceptor group by a π-conjugatedgroup. The electron acceptor is a sulfone group containing a substituentselected from the group consisting of alkyl, hydroxyalkyl, andalkyl(meth-)acrylate moieties. The sulfone group is represented by theformula: ##STR2## where D is the electron donor group, π represents theconjugated group, and R₁ is one of the noted substituents.

The use of D, R₁, and R¹ -R⁷ above to describe the compounds disclosedin U.S. Pat. Nos. 4,973,429 and 5,006,729 is not to be confused with theuse of similar notation below to describe the present invention.

SUMMARY OF THE INVENTION

This invention provides a new composition of matter for generatingsecond-order NLO responses. The new composition comprises PDFMsincorporated in and aligned noncentrosymmetrically in an optically clearpolymeric composition.

In another aspect, this invention provides a process for preparing a NLOcomposition, which comprises incorporating PDFMs in an optically clearpolymer and aligning the incorporated PDFMs noncentrosymmetrically.

In a further aspect, this invention provides a method of generating asecond-order NLO response, which comprises passing light through a NLOcomposition containing an optically clear polymeric composition havingPDFMs incorporated therein and being aligned noncentrosymmetrically.Preferred light wavelengths for use with the NLO compositions of thisinvention range from about 400 to 2000 nm, more preferably from 600 to1600 nm.

In a still further aspect, this invention provides a polymer having aplurality of polar moieties covalently bonded thereto, the polarmoieties comprising: an electron-withdrawing group comprising adisulfone group; an electron-donating group; and a conjugated grouplocated between the electron-withdrawing and donating groups.

In an additional aspect, this invention provides new PDFMs and a newprocess for preparing PDFMs. The new PDFMs are described below in thedetailed description of this invention. The new process for preparingPDFMs comprises reacting vinyl ether disulfone molecules, enaminedisulfone molecules, or alkenyl disulfone molecules having an activatedmethyl or methylene group with molecules having an electron-donatinggroup, with the provisos that: (i) if the reactants include vinyl etherdisulfone molecules, the molecules having the electron-donating groupinclude activated aromatic molecules, activated heterocyclic molecules,dye bases, or dye olefins; (ii) if the reactants include enaminedisulfone molecules, the molecules carrying the electron-donating groupinclude dye bases or dye olefins; and (iii) if the reactants includealkenyl disulfone molecules having an activated methyl or methylenegroup, the molecules having the electron-donating group includealdehydes or acetals derived therefrom.

In this invention, it has been discovered that an optically clearpolymeric composition having PDFMs incorporated therein will providesecond-order NLO effects when the PDFMs have been alignednoncentrosymmetrically. It has also been discovered that thePDFM-incorporated compositions absorb light over a relatively narrowband of wavelengths. The latter discovery is particularly significant,because it is very desirable that minimal amounts of light be absorbedby the NLO compositions at the preferred wavelengths at which the NLOcompositions operate. Having this advantage, the NLO compositions ofthis invention will be useful over a relatively greater range ofwavelengths for NLO applications.

As used herein:

"disulfone-functionalized" and "disulfone group" means a molecular grouphaving two --SO₂ -- radicals attached to the same carbon atom;

"dye base" means a compound derived from a quaternized heterocyclicammonium salt and containing an electrophilically-reactive olefinicmethylene or methine group conjugatively located to the nitrogen atom ofthe ammonium salt;

"dye olefin" means a 1,1-diaryl ethylene having an electron-donatinggroup conjugatively located to the ethylene group, wherein the olefinicmethylene group is electrophilically reactive;

"electron-donating" means a group that contributes to the electrondensity of a π-electron system;

"electron-withdrawing" means a group that attracts electron density froma π-electron system;

"optically clear" means possessing an attenuation of less than five (5)decibels per centimeter (dB/cm); and

"polar" means possessing a dipole moment.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of an apparatus for generating anddetecting second harmonic light.

FIG. 2 is a schematic representation of an apparatus for providingelectro-optic modulation of polarized light.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION

In a preferred embodiment, the present invention includes a NLOcomposition having PDFMs incorporated in an optically clear polymericcomposition, where the incorporated PDFMs are alignednoncentrosymmetrically and have (i) an electron-withdrawing groupcomprising a disulfone group, (ii) an electron-donating group, and (iii)a conjugating group located between the electron-withdrawing anddonating groups. The conjugating group preferably has from 1 to 6 doublebonds, more preferably from 2 to 5 double bonds. As the term is usedherein, "double bonds" includes the "resonance bonds" of aromatic andhetero-aromatic nuclei, represented in the Kekule fashion.

The electron-donating nature of a chemical may be determined by avariety of methods. The Hammett sigma value (σ) is an accepted measureof a group's electron-donating ability, especially the sigma para value(σ_(p)) under conditions of conjugation as shown, for example, by O.Exner in "Advances in Linear-Free-Energy Relationships", edited by N. B.Chapman and J. Shorter, Plenum Publ., N.Y., N.Y. (1972), particularlypages 28-30, 41-45, and 50-52. A group in the para-position that has aσ_(p) value less than zero has an electron-donating ability that isuseful in the present invention. It is preferred, however, that theelectron-donating group of the PDFM have a σ_(p) value of less than-0.3, more preferably less than -0.5. An electron-donating group in theortho-position is also useful in the present invention, though somewhatless so, as a rule.

The PDFMs may be represented by the Formula: ##STR3## where

n is 0, 1 or 2, preferably 1 or 2;

R¹ and R² each independently represent hydrogen, an alkyl group of about1 to 4 carbon atoms (for example, methyl, ethyl, propyl, isopropyl,butyl, and sec-butyl), or taken together in conjunction with thecatenary carbon atoms therebetween form a 5 or 6-membered carbocyclic orheterocyclic ring, when n is 2, and R¹ and R² may variously combine withthe catenary carbon atoms to form a 5 or 6-membered carbocyclic orheterocyclic ring(s) (viz., R¹ and R², R¹ and R¹, or R² and R², maycombine with the catenary carbon atoms to form the 5 or 6 memberedcarbocyclic or heterocyclic ring(s));

R_(f) ¹ and R_(f) ² each independently represent fluorine, a saturatedfluorinated alkyl group containing 1 to 10 carbon atoms, preferably 1 to4 carbon atoms, or taken together in conjunction with the disulfonegroup may represent a 5, 6, or 7-membered ring containing two, three, orfour carbon atoms, respectively, which are fluorinated, preferablyhighly fluorinated, more preferably perfluorinated (perfluorinated meansthat all hydrogen atoms bonded to carbon atoms have been replaced withfluorine atoms);

and Z represents: an aryl group that bears an electron-donatingsubstituent; an activated heterocyclic aromatic group; a group derivedfrom a dye base; or a group derived from a dye olefin.

No particular double bond geometry (for example, cis or trans) isintended by the structure of Formula I or any of the other formulasshown below.

When R_(f) ¹ and R_(f) ² represent saturated fluorinated alkyl groups of1 to 10 carbon atoms, there may also be atoms other than fluorine bondedto the carbon atoms, such as halogens (for example, chlorine) orhydrogen. It is preferred that a majority of the carbon atoms adjacentand next-adjacent to the --SO₂ -- groups in R_(f) ¹ and R_(f) ² befluorinated, and more preferably be perfluorinated. Preferably, not morethan one atom bonded to each carbon atom is not a fluorine atom. Morepreferably, R_(f) ¹ and R_(f) ² are CF₃, especially when a molecularweight limitation exists, as for example, when attempting to maximizethe number of NLO-active molecular groups per unit volume of the NLOcomposition. A saturated fluoroaliphatic group may be a straight orbranched chain, cyclic, or a straight chain including a cyclic group.Additionally, the fluoroaliphatic group may contain an oxygen atomlinking two carbon atoms, for example, --CF₂ OCF₂ --, or a nitrogen atomlinking three carbon atoms, for example, (--CF₂ (CF₃ )NCF₂ --).Exemplary fluoroaliphatic groups include perfluoromethyl,perfluoroisopropyl, perfluorobutyl, perfluorooctyl, perfluorododecyl,perfluoro-(4-ethylcyclohexyl), omega-chloroperfluorohexyl),2-hydroperfluoropropyl, and perfluoro-(3-N-morpholinopropyl). Inaddition, and as noted above, R_(f) ¹ and R_(f) ² may be joined to formgroups such as --CF₂ --CF₂ --, --CF₂ --CF₂ --CF₂ --, and --CF₂ --CF₂--CF₂ --CF₂ --. In such cases, a 5, 6, or 7-membered ring results.

When Z represents an aryl group that is substituted with anelectron-donating group, that group may be represented by the Formula:##STR4## where

Ar- represents a monovalent aryl group having 6 to 10 ring atoms;

Y represents a monovalent electron-donating substituent group having upto about 20 atoms (preferably conjugatively located relative to theconjugated system extending between the electron donating and electronwithdrawing groups) such as an amino group represented by the formula R³R⁴ N--, an ether or thioether group having the formula R³ O-- or R³ S--,where R³ and R⁴ independently represent a monovalent alkyl of 1 to 12carbon atoms (preferably 1 to 4 carbon atoms), cyanoalkyl of 1 to 4carbon atoms (preferably cyanomethyl or cyanoethyl), an aryl, alkaryl,or arylene group having 6 to 10 ring atoms (preferably phenyl, tolyl, orphenylene) and having less than about 15 total carbon atoms, analkylene, alkyleneoxy, alkylene-tert-amino, or alkylenethio group of 1to 3 carbon atoms, an alkyleneacylamino having 1 to 3 ring atoms, anaralkyl group (such as benzyl) of up to about 15 total carbon atoms, orR³ and R⁴ taken together in conjunction with the nitrogen atom (andoptionally adjacent positions on the conjugated aromatic ring) form oneor more 5 or 6-membered heterocyclic rings;

X represents a monovalent substituent group having 1 to about 20 atoms,for example, a halo such as fluoro, chloro, bromo, or iodo, asubstituted or unsubstituted aryl group Ar- as defined above, where Ar-may be substituted (for example, with an electron-donating group Y asdefined above) a lower alkyl or a substituted lower alkyl having from 1to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, and4-chlorobutyl, an alkoxy group having from 1 to 4 carbon atoms such asmethoxy, ethoxy, n-propoxy, or isopropoxy, a haloalkyl having from 1 to4 carbon atoms such as 4-chlorobutyl or chloromethyl, an acyloxy grouphaving from 1 to 4 carbon atoms such as acetoxy or buryfoxy, anacylamido having from 1 to 10 carbon atoms such as N-ethyl acetamido,saturated cyclics or heterocyclics having from 3 to 10 carbon atoms suchas 2,3-methylenedioxy, 2,3-trimethylene, or 2,3 tetramethylene, analkylthio group having from 1 to 10 carbon atoms such as methylthio,ethylthio, propylthio, acetylthio, an aryl or substituted aryl having 6to 10 ring atoms such as phenyl, m-tolyl, p-anisyl, an aralkyl grouphaving from 7 to 15 carbon atoms such as benzyl, an alkenyl having 2 to15 carbon atoms, or an aralkenyl group having from 8 to 15 carbon atoms,for example β-styryl, allyl, etc.;

k is 1 or 2, preferably 1; and

m is an integer of 0 to 6 ("0" is considered herein to be an integer).

It is to be understood that, when k is 2, or m is 2 or greater, each Yand each X, respectively, may be different from each other. For example,if k is 2, a first Y could be (C₂ H₅)₂ N-- and a second Y could be C₂ H₅O--.

Examples of aryl groups of the Formula II include4-dimethylamino-1-naphthyl, 6-chloro-4-diethylamino-1-naphthyl,2,4,5-trimethoxyphenyl, 2-fluoro-4-dimethylaminophenyl,3-fluoro-4-dimethylamino-5-ethoxyphenyl, 3,4-methylenedioxyphenyl,2-chloro-4-N-pyrrolidinophenyl, N-butyl-5-indolino,N-ethyl-6-(1,2,3,4,-tetrahydro)quinolino,N'-(2''-ethylhexyl)-4(N-piperazino) phenyl, 2,4-bis(methylthio)phenyl,2-methyl-4-(4'-methylpiperidino)phenyl,4-(N-2'-chloroethyl-N-propylamino)phenyl, 4-(N-methylacetamido)phenyl,2-(N-piperidino)phenyl, 4-(N'-phenylpiperazino)phenyl,4-(N-morpholino)phenyl, 4-(N-pyrrolidino)-3-fluorophenyl, and4-julolidino.

when Z represents an activated heterocyclic aromatic group, that groupmay be represented by the Formula: ##STR5## where ##STR6##

represents a monovalent heterocyclic aromatic nucleus containing 5 or 6ring atoms;

V represents X, or, taken together with atoms in the monovalentheterocyclic nucleus, V represents the necessary atoms to complete a6-membered aromatic nucleus;

g is an integer of 0 to 4;

and E is S, O, or NR⁵, preferably NR⁵, where R⁵ represents a substituentcontaining up to about twenty carbon atoms (preferably 1 to 10, morepreferably 1 to 4), preferably selected from the group consisting of: anacyclic hydrocarbon substituent (substituted or unsubstituted)preferably aliphatic such as an alkyl group (including substitutedalkyl) preferably containing from 1 to 13 carbon atoms, for example,methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, hexyl, cyclohexyl,decyl, dodecyl, octadecyl, alkoxyalkyl (for example, methoxyethyl),hydroxyalkyl (for example, ω-hydroxyethyl, ω-hydroxypropyl, etc.); analkenyl substituent such as allyl, 1-propenyl, 2-propenyl, 1-butenyl,2-butenyl and 3-butenyl, etc.; an alkaryl substituent such as benzyl andβ-phenylethyl; and an aryl substituent such as phenyl, p-tolyl, o-tolyl,3,4-dichlorophenyl, paramethoxyphenyl, etc.

Representative examples of activated heterocyclic aromatic groupsinclude N-butyl-2,4,5-trimethylpyrrolo,N-(3,4-dichlorophenyl)-2,5-dimethylpyrrolo, N,2-dimethyl-3-indolo,5-dimethylamino-2-thienyl, 4,5-dimethyl-2-thienyl,N-(2'-cyanoethyl)-2,5-dimethyl-3-indolo, andN-methyl-2,5-diphenylpyrrolo.

When Z represents a group derived from a dye base, that group may berepresented by the Formula: ##STR7##

where p is 0, or 1; R⁵ is as defined above; and

W represents the non-metallic atoms required to complete a heterocyclicnucleus containing from 5 or 6 atoms in the heterocyclic ring, which mayalso include in addition to the hetero nitrogen atom, a second heteroatom such as a second nitrogen atom, an oxygen atom, a selenium atom, ora sulfur atom. W also can be further substituted, for example, to formadditional rings on the heterocyclic nucleus.

Representative heterocyclic nuclei from which the heterocyclic group maybe derived include: a thiazole nucleus, for example, thiazole,4-methylthiazole, 4-phenyl-thiazole, 5-methylthiazole, 5-phenylthiazole,4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)thiazole,etc.); a benzothiazole nucleus (for example, benzothiazole,4-chlorobenzothiazole, 5-cblorobenzothiazole, 6-chlorobenzothiazole,7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole,6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole,4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole,5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole,6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole,tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole,5,6-dioxymethylenebenzothiazole, etc.); a naphthothiazole nucleus (forexample, α-naphthothiazole, β-naphthothiazole,5-methoxy-β-naphthothiazole, 5-ethoxy-β-naphthothiazole,8-methoxy-α-naphthothiazole, 7-methoxy-α-naphthothiazole, etc.); athianaphtheno-7', 6', 4,5-thiazole nucleus (for example,4'-methoxythianaphtheno-7', 6', 4,5-thiazole, etc.); an oxazole nucleus(for example, 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole,4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole,5-phenyloxazole, etc.); a benzoxazole nucleus (for example, benzoxazole,5-chlorobenzoxazole, 5-methylbenzoxazole, 5 -phenylbenzoxazole,6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole,5-methoxybenzoxazole, 5-ethoxybenzoxazole, 6-chlorobenzoxazole,6-methoxybenzoxazole, etc.); a naphthoxazole nucleus (for example,α-naphthoxazole, β-naphthoxazole, etc.); a selenazole nucleus (forexample, 4-methylselenazole, 4-phenylselenazole, etc.); abenzoselenazole nucleus (for example, benzoselenazole,5-chlorobenzoselenazole, 5-methoxybenzoselenazole,4,5,6,7-tetrahydrobenzoselenazole, etc.); a naphthoselenazole nucleus(for example, α-naphthoselenazole, β-naphthoselenazole, etc.); athiazoline nucleus (for example, thiazoline, 4-methylthiazoline, etc.);a 2-quinoline nucleus (for example, quinoline, 3-methylquinoline,5-methylquinoline, 7-methylquinoline, 8-methylquinoline,6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline,6-ethoxyquinoline, 3,4-dihydro-3,3-dimethylquinoline, etc.); a4-quinoline nucleus (for example, quinoline, 6-methoxyquinoline,7-methylquinoline, 8-methylquinoline, etc.); a 1-isoquinoline nucleus(for example, isoquinoline, 3,4-dihydroisoquinoline, etc.); a3-isoquinoline nucleus (for example, isoquinoline, etc.); a3,3-disubstitutedindolenine nucleus (for example,3,3-dimethylindolenine, 3,3,5-trimethylindolenine,3,3,7-trimethylindolenine, etc.); a 2-pyridine nucleus (for example,pyridine, 3-methylpyridine, 6-methylpyridine, 5-ethylpyridine,3,5-dimethylpyridine, 3-chloropyridine, 5-phenylpyridine, etc.); a4-pyridine nucleus (for example, 2-methylpyridine, 3-methylpyridine,3-chloropyridine, 2,6-dimethylpyridine, etc.); a 1-alkyl-2-imidazolenucleus (for example, 1-methylimidazole, 1-ethyl-4-phenylimidazole,1-butyl-4,5-dimethylimidazole, etc.); a 1-alkyl-2-benzimidazole nucleus(for example, 1-methylbenzimidazole, 1-butyl-4-methylbenzimidazole,1-ethyl-5,6-dichlorobenzimidazole, etc.); a 1-alkyl-2-naphthimidazolenucleus (for example, 1-ethyl-α-naphthimidazole,1-methyl-β-naphthimidazole, etc.); and an imidazoquinoxaline nucleus(for example, an imidazo[4,5-b]quinoxaline.

When z represents a group derived from a dye olefin, that group may berepresented by the formula: ##STR8## where Ar, Y, X, and m are asdefined above; Ar' independently represents Ar (that is, Ar' may be thesame or different from Ar) Y' and X' independently represent Y and X,respectively; m' independently represents m, and h and h' independentlyrepresent 0, 1, or 2, preferably 1, with the proviso that both h and h'cannot be zero. It being understood that when h and h' are equal to 2,and m' is 2 or greater, each Y, Y' and X', respectively, may bedifferent from each other.

Representative examples of dye olefin groups include:2-phenyl-2-(4'-N,N-diethylaminophenyl)vinyl;2-(4'-ethoxyphenyl)-2-(4''-N,N-dimethylaminophenyl)vinyl; and2,2-bis-(4'-N,N-dimethylaminophenyl)vinyl.

PDFMs may be incorporated into a polymeric composition by (1)molecularly dispersing the PDFMs in the polymeric composition (aguest-host relationship), or (2) chemically reacting the PDFMs with apolymeric composition or with precursors to a polymeric composition. Asthe term is used herein, "incorporated" means the PDFMs are placed in apolymeric composition by either of these two methods.

In the first method, guest PDFMs may be incorporated into a hostpolymeric composition by, for example, forming a solution containingguest PDFM molecules, host polymeric composition, and solvent. Thesolution can be formed in a variety of ways; for example, PDFMs may bedissolved in a suitable solvent followed by adding a host polymer (orthe order can be reversed), or the PDFMs and a host polymer may bedissolved together in a solvent. Suitable solvents may include organicsolvents such as 1,2-dichloroethane, butyl acetate, acetone,chlorobenzene, chloroform, and mixtures thereof. After the solution isformed, the NLO molecules can be aligned noncentrosymmetrically by, forexample, applying the solution to a substrate, removing the solvent, andpoling the polymeric composition with a DC electric field. These stepsare described below in more detail.

It may also be possible to incorporate guest PDFMs into a host polymericcomposition without using a solvent. This might be accomplished, forexample, by dissolving guest PDFMs in a molten host polymer, or bydissolving PDFMs in monomers that react to form a host polymer.

Any optically clear polymeric composition may be employed as a host inthe NLO guest-host compositions this invention. Preferred opticallyclear polymeric compositions form chemically and environmentally stableNLO compositions, and have a T_(g) that is greater than the maximaltemperature of use of the NLO composition. More preferred polymericcompositions have a T_(g) that is about 30° C. higher (yet morepreferably 50° C. higher) than the temperature at which the NLOcompositions are used. It is preferred that the T_(g) of the polymericcomposition be greater than about 80° C. It is also preferred that theguest-host polymeric composition be one that remains in an amorphous andglassy state throughout use of the NLO composition. Polymericcompositions that are amorphous and glassy are those that exhibit aglass transition temperature and have no significant melting point orx-ray evidence of crystallinity.

Examples of polymeric compositions that may be suitable as opticallyclear polymeric hosts include: polymers and copolymers of acrylates suchas polyacrylates and polymethacrylates such as poly(methylmethacrylate)(PMMA); epoxy resins; polystyrene and derivatives and copolymersthereof; polycarbonates such as bisphenol-A-polycarbonate and copolymersthereof; and glassy polyesters such as amorphous (unoriented)poly(oxyethyleneoxyterephthaloyl),poly(oxyethyleneoxycarbonyl-1,1,3-trimethylindan-3,5-ylene-1,4-phenylenecarbonyl),poly(oxyisophthaloyloxy-1,4-phenyleneisopropylidene-1,4-phenylene),poly(oxy-1,4-phenylenefluoren-9-ylidene-1,4-phenyleneoxysebacoyl),poly(oxy-1,3-phenyleneoxyisophthaloyl),poly(oxypropylen-oxycarbonyl-2,6-napthylenecarbonyli, orpoly(oxy-2,2,4,4-tetramethyl-1,3-cyclobutyleneoxycarbonyltrans-1,4-cyclohexylenecarbonyl);and glassy polyurethanes and polyamides such aspoly(oxyethyleneoxycarbonylimino-1,4-phenylenemethylene-1,4-phenyleneiminocarbonyl),poly(oxytrimethyleneoxycarbonylimino-1,4-phenyleneethylene-1,4-phenyleneiminocarbonyl),poly(iminoadipoylimino-1,4-cyclohexylenemethylene-1,4-cyclohexylene),poly(imino-1,3-phenyleneiminosebacoyl),poly(sulfonyl-1,3-phenyleneiminoadipoylimino-1,3-phenylene), orpoly(iminohexamethyleneiminocarbonyl- 2,2'-biphenylenecarbonyl); andcopolymers among the polyesters, polyamides, and polyurethanes. Otherpotentially-useful polymers are disclosed in J. Brandrup et al., PolymerHandbook, John Wiley and Sons, Inc. (1975). Weight percentages of guestPDFMs in the guest-host polymeric composition range from about 1 to 70percent, preferably 10 to 30 percent.

In the second method, PDFMs may be incorporated into an optically clearpolymeric composition through a chemical reaction(s), which results inthe formation of a polymeric composition that has covalently-bonded,polar moieties that each have a disulfone group. It is preferred toincorporate the PDFMs into a polymeric composition by this method (asopposed to dispersing the PDFMs in a polymeric composition) because,after poling, the covalently-bonded polar moieties are better able tohold their aligned positions in the resulting polymeric composition. Ina guest-host composition, the dispersed PDFMs have a greater tendency torotate and lose their alignment.

PDFMs may become covalently bonded to a polymeric composition by, forexample, reacting PDFMs with a polymer. In another embodiment, PDFMs maybe reacted with precursors to a polymer. For example, PDFMs may bereacted with polymerizable molecules to form monomers possessing polarmoieties containing disulfone groups. These monomers may then bepolymerized to form a polymer that possesses polar moieties containingdisulfone groups. The polymers resulting from these noted reactions havea plurality of polar moieties covalently bonded thereto. The polarmoieties each have an electron-withdrawing group comprising a disulfonegroup, an electron-donating group, and a conjugated group locatedbetween the electron-withdrawing and donating groups. These resultingpolymers are considered to be new compositions of matter.

PDFMs and a polymer may be reacted so that the polar moieties (withdisulfone functionality) become covalently bonded to the backbone orside chains of the polymer. This may be accomplished, for example, bydissolving PDFMs with a reactively-compatible polymer in a suitablesolvent and preferably warming this solution under an inert atmospheresuch as dry nitrogen. The solution preferably is warmed to a temperatureof from about 50° to 200° C. (120° to 400° F.). The reaction temperaturemay vary depending on, for example, the solvent used, the reactivity ofthe PDFMs, and the reactivity of the polymer. In one method ofattachment, a base is added to catalyze the reaction and/or toneutralize acid generated in the course of the reaction. Preferred basesinclude anhydrous pyridine, anhydrous trialkyl amine, and/or othernon-nucleophilic nitrogen bases. The reaction mixture then, preferably,is heated to or near the boiling point of the solvent. After thereaction is sufficiently complete (typically in about 1 to 24 hours),the reaction mixture is cooled, and product precipitation may beinduced, preferably, by adding a non-solvent for the polymer, forexample, an alcohol such as methanol or ethanol, or water whereappropriate.

A variety of solvents may be used in a reaction between PDFMs and apolymer. The solvent selected preferably dissolves the PDFMs and polymerand is not deleterious to the reaction. Preferably, the solvent is anorganic solvent such as tetrahydrofuran, ethyl or butylacetate,1,4-dioxane, 1,2-dichloroethane, chloroform, acetonitrile, toluene, or amixture thereof.

A polymer selected as a reactant preferably is one that forms anoptically-clear polymeric composition having a polar disulfonefunctionalized moiety attached thereto. Representative examples ofpolymers that may be useful for reactions with PDFMs include (but arenot limited to): reactive vinyl polymers (including copolymers) such aspolyvinyl alcohol, poly(styrene-co-maleic anhydride),poly(methylvinylether-co-monobutylmaleate),poly(methylmethacrylate-co-methacrylic acid), and polymers (includingcopolymers) of acrylic acid, methacrylic acid, hydroxyethyl acrylate,hydroxyethyl methacrylate, isocyanatoethyl methacrylate, acryloylchloride, and methacryloyl chloride; condensation polymers such aspolysiloxanes, polyesters, and polyamides possessing further reactivesites, for example, poly(methyl-3-aminopropylsiloxane), and copolymersthereof such as poly(dimethylsiloxane-co-methyl-3-aminopropyl siloxane);and reactive polypeptides and co-polypeptides such as poly(glutamicacid), and co-polypeptides thereof. Other representative examples ofpolymers include (but are not limited to) modified versions of reactivenatural polymers such as cellulose, for example, (hydroxyethyl)cellulose, (hydroxypropyl) cellulose, and (carboxymethyl) cellulose.

As indicated above, a PDFM may be reacted with polymerizable moleculesto form monomers possessing polar moieties that contain disulfonegroups. These monomers can then be polymerized to form a polymericcomposition of this invention. This method may be accomplished, forexample, by reacting a PDFM, such as,1,1-bis(trifluoromethanesulfonyl)-2-(4-N-hydroxyethyl-N-ethylamino)phenyl)ethane,with a polymerizable molecule, for example, methacryloyl chloride, in asuitable solvent under an inert atmosphere. The newly-created monomer, amethacrylated PDFM, can be subsequently polymerized by a suitablepolymerization mechanism, such as free radical polymerization, toproduce a polymeric composition that contains polar moieties that eachhave a disulfone group.

Solvents suitable for the reaction between PDFMs and polymerizablemolecules include the solvents described above for the reaction betweenthe PDFMs and a polymer. Reaction temperatures are estimated to rangefrom about 50° to 200° C. (120° to 400° F.), but may vary depending forexample, the solvent used and the reactivity of the PDFMs and thepolymerizable molecules.

Examples of other polymerizable molecules that may be used to form aPDFM-incorporated polymer include: reactively-substituted styrenes, suchas parahydroxystyrene and chloromethylstyrene; acrylates andmethacrylates such as 2-hydroxyethylacrylate,2-hydroxyethylmethacrylate, and 2-aminoethylmethacrylate; and vinylazlactones such as 2-vinyl-4,4-dimethyl-2-oxazolin-5-one (also called2-vinyl-4,4-dimethylazlactone (VDM)),2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one,2-vinyl-4,4-diethyl-2-oxazolin-5-one,2-vinyl-4-ethyl-4-methyl-2-oxazolin- 5-one,2-vinyl-4-dodecyl-4-methyl-2-oxazolin-5-one,2-vinyl-4,4-pentamethylene-2-oxazolin-5-one,2-vinyl-4-methyl-4-phenyl-2-oxazolin-5-one,2-isopropenyl-4-benzyl-4-methyl-2-oxazolin-5-one, and2-vinyl-4,4-dimethyl-1,3-oxazin-6-one; isocyanatoalkyl esters such as2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate; andisocyanate-functional monomers such as m- or p-isopropenylcumylisocyanate (available from American Cyanamid, Stanford, Conn.) havingthe structural formula: ##STR9## Useful azlactone monomers are describedin U.S. Pat. No. 4,378,411 and in "Polyazlactones", Encyclopedia ofPoly. Sci. and Engn., 1988 11, 558-571, 2nd Ed., Wiley, N.Y., both ofwhich are incorporated here by reference.

Polymers possessing polar moieties that include disulfone groups maycontain units represented by the Formula: ##STR10## where P¹ and P²represent polymer main chain units; L is a linking group having 1 to 20chain atoms, preferably 1 to 6; D is a polar moiety comprising adisulfone group, which polar moiety preferably comprises at least about10 weight percent of the polymer, more preferably at least 30 weightpercent; j is 0 or 1; and x represents the molar fraction of units--(L)_(j) --D bonded to the polymer backbone, preferably at least 0.01,more preferably at least 0.1, and even more preferably at least 0.3. Atthe upper end, x is preferably less than 0.8, and more preferably lessthan 0.5. Novel polymers of this invention preferably have a numberaverage molecular weight that permits the polymer to form a film orlayer. It is estimated that such polymers would have a molecular weightin the range of about 2,000 to 100,000.

Examples of linking groups L include (but are not limited to) organicgroups containing ester, ether, thioether, alkylene, amide, carbonate,urethane, and urea moieties, and combinations and oligomers thereof, forexample: ##STR11## where: q and q' independently represent an integer offrom 0 to 12, preferably 1 to 10, more preferably 2 to 8; and R⁶ and R⁷independently represent H, or C_(r) H_(2r+1), where r is an integer offrom 1 to 4.

Polymeric compositions having PDFMs incorporated therein may be coatedonto suitable substrates by known methods to form a layer of thepolymeric composition. Suitable substrates may be inorganic, such assilicon wafers or glass, or may be organic, such as polymeric flatplates comprised of polymethylmethacrylate (PMMA), polycarbonates, epoxyresins, etc. An electrically-conductive substrate can serve as anelectrode in an electro-optic device of the invention. Compositionshaving the PDFMs incorporated therein may be applied to a substrate, forexample, in any of the ways known in the art, such as pouring, casting,roller coating, spraying, and spin coating. To apply a NLO compositionto a substrate using these methods, the polymeric composition preferablyis dissolved in a volatile solvent(s). Examples of solvents includeorganic polar solvents such as 1,2-dichloroethane, butyl acetate,acetone, chlorobenzene, chloroform, and mixtures thereof. Typical weightproportions of polymer in solution may range from about one to twentypercent or higher, as may be appropriate for the chosen applicationtechnique.

After applying the polymeric composition to a substrate, the solvent isremoved, for example, by evaporation at room temperature, followed bycontrolled heating for several hours. Preferably, the polymericcomposition is heated above to its T_(g) to facilitate removal of thesolvent. This heating preferably takes place in a vacuum oven.

The resulting composition (without the solvent) may be used on thesubstrate as a NLO device, or the composition may be removed from thesubstrate and used as a self-supporting NLO layer. Typically, it ispreferred that the NLO layer be used on a substrate and have a uniformthickness. Adequate uniformity in a NLO layer typically can be achievedby having thickness variations of less than 5 micrometers, preferablyless than 0.5 micrometers, and more preferably less than 0.05micrometers. It is desired that the thickness variations be less thanthe wavelength of light passing therethrough. Uniformity is particularlydesirable when light is passed through the layer in a direction parallelto the plane of the NLO layer. If the layer's thickness is not uniformin this instance, there is a possibility that the performance of the NLOdevice would be compromised in that light passing through the layer maysustain mode-mixing and might escape therefrom. Uniformity is not asessential when light is passed perpendicularly through the NLO layer.

It is also preferred that the NLO layer be transparent to incoming andoutgoing light. If the applied layer is not transparent to incoming andoutgoing light, the NLO device will absorb radiation; its effectivenesswill be severely reduced, if not entirely lost. Adequate lighttransparency may be achieved by using a layer having an attenuation ofnot greater than five (5) dB/cm, preferably less than 1 dB/cm, for thechosen wavelengths of operation. Layer thicknesses generally range fromabout 0.1 to 10 micrometers, preferably from 0.5 to 3 micrometers.

Noncentrosymmetric alignment of the incorporated PDFMs may beaccomplished by "poling" the polymeric composition under conditionsfavorable to molecular rotation. There are a variety of methods (knownto those skilled in the art) to pole NLO compositions. Known methodsinclude planar gap poling, sandwich electrode poling, and corona poling.In the planar gap method, the composition is placed in solution and isspin coated across a gap between two coplanar electrodes. The solvent isremoved, and an external field is applied across the electrode gap at atemperature above the composition's T_(g). Alternatively, the appliedlayer can be sandwiched between two electrodes to pole the PDFMs in adirection perpendicular to the plane of the applied layer, or a surfacecharge may be deposited by corona discharge onto the polymericcomposition's surface. The incorporated PDFMs are preferably poled usinga DC electric field to an extent that the poled composition's χ.sup.(2)is measured to be about 10⁻⁹ electro static units (esu), preferably 10⁻⁷esu, and more preferably 10⁻⁶ esu.

FIG. 1 shows an apparatus 10 for providing second harmonic generation oflight. Light of frequency w from laser source 2 is incident on poledlayer 4, and light of frequency 2w is created within layer 4, exitslayer 4, and is subsequently detected. Two light beams exit layer 4, oneat frequency 2w, and another at frequency w. The emerging light issuccessively passed through collection lens and color filter 6 to removelight of frequency w. Light of frequency 2w then passes throughmonochromator 8, and signal detector 12. The light of frequency 2w canbe used for optical purposes such as optical memories, laserspectroscopy, photochemical reactions, or photo-reproduction. Otherfactors being appropriately controlled, the SHG intensity at frequency2w provides a measure of the sheet's SHG χ.sup.(2) effect. It ispreferred that the light used for SHG be coherent and monochromatic.

FIG. 2 shows an apparatus for providing an electro-optic effect.Incident light (preferably monochromatic) of frequency w from laser 2 issuccessively passed through polarizer 22, phase compensator 24, focusinglens 26, and NLO layer 4 connected to modulation source 28. Lightemerging from layer 4 is passed through collimating lens 30,polarization analyzer 32, and detector 34.

An applied electric field from modulation source 28 induces abirefringence in layer 4. The induced birefringence causes lightpolarizations parallel and perpendicular to the applied field to shiftin phase with respect to one another. As the applied voltage is altered,the intensity of the light passing through the apparatus is alsoaltered. This change in intensity as a function of the applied voltageprovides a measure of the NLO layer's electro-optic χX.sup.(2) effect.

Compositions and devices disclosed above may be used for manipulatingthe direction, frequency, amplitude, and phase of light such as coherentmonochromatic light from a laser. For example, the NLO composition ofthis invention can be applied to a substrate in the form of a uniformthin layer to produce a waveguide, or as noted above, the compositionmay be applied to a substrate to form a second harmonic generator or maybe applied to a substrate and have electrodes attached thereto to forman electro-optic switch.

PREPARATION OF PDFMS

Known PDFMs have been prepared by methods disclosed in U.S. Pat. Nos.3,932,526, 3,933,914, 3,984,357, 4,018,810, 4,069,233, and 4,156,696.The disclosures of these patents are incorporated here by reference. Inthe known methods, PDFMs are typically prepared by reacting an aldehydeand bis(perfluoroalkylsulfonyl)methane in a Knoevenagel reaction. Theprior art methods are, however, limited in usefulness because thealdehyde reactants are costly or frequently unavailable and/or aretroublesome or difficult to prepare. In the prior art methods, thealdehyde reactants typically are donor-substituted benzaldehydes orcinnamaldehydes or may be heterocycles or dye bases conjugativelybearing an aldehyde group. The following new method for preparing PDFMsavoids problems associated with the use of such aldehydes as startingmaterials.

In the new method, a vinyl ether disulfone molecule, an enaminedisulfone molecule, or an alkenyl disulfone molecule is reacted with amolecule carrying an electron-donating group to form a PDFM. This newmethod is advantageous in that the disulfone reactant has a groupcomprising 1 to 3 double bonds attached to the disulfone group (thedouble bonds being conjugated when there is more than one). Using adisulfone reactant having such a molecular structure, prior art problemsof attaching conjugated groups to the electron donating reactant areavoided.

When the disulfone reactant is a vinyl ether disulfone molecule, themolecule carrying the electron-donating group may be an activatedaromatic compound, an activated heterocyclic compound, a dye base, or adye olefin. As the term is used here, "activated" means the compoundsare more susceptible to electrophilic substitution on the aromaticring(s) than is anisole.

When the disulfone reactant is an enamine disulfone molecule, thereactant carrying the electron-donating group normally may not be anactivated aromatic compound; however, a dye olefin or a dye base may beused to form a PDFM.

When using a dye base in a reaction with a vinyl ether disulfone or anenamine disulfone, it may be convenient to generate the dye base from aprecursor in situ, for example, by reacting the dye base's hydrochloridewith a base such as a tetraalkylammonium hydroxide, an alkali hydroxide,an amine, or the like, preferably an amine, and more preferably atertiary amine.

When the disulfone reactant is an alkenyl disulfone molecule having atleast two reactive allylic hydrogens as, for example, a vinylogousmethyl group, the molecule carrying the electron-donating group may bean aldehyde or an acetal derived therefrom and preferably an aromaticaldehyde or an aromatic acetal derived therefrom: preferably having from5 to 10 ring atoms, such as a substituted benzaldehyde, a "vinylog"thereof such as a cinnamaldehyde or acetals derived from such aldehydes.The aldehyde can also be a dye base aldehyde or a dye olefin aldehyde(that is, a dye base or a dye olefin bearing an aldehyde group on theactive olefinic position) or acetals derived from such aldehydes. Thisreaction may be used when the molecule carrying the electron-donatinggroup does not have an amine activating group, and especially when anaromatic acetal is available.

Described below are examples of reactions for forming PDFMs according tothe method of this invention.

When the disulfone reactant is a vinyl ether disulfone molecule, a PDFMmay be formed according to the following reaction schemes (ia-id):##STR12## where R¹, R², R_(f) ¹, R_(f) ², R⁵, W, Ar, Ar', X, Y, X', Y',h, h', m, m', g, n and p are as provided above, R⁸ represents hydrogenor a monovalent organic radical, preferably a lower alkyl radical of 1to 4 carbon atoms and more preferably hydrogen, R⁹ represents amonovalent organic acyl, allyl, aryl, alkyl, or aralkyl radical,preferably having 1 to 8 carbon atoms, preferably an acyl or alkylgroup, preferably from 1 to 4 carbon atoms, and A.sup.θ represents amonovalent anion, for example, chloride, bromide, iodide,p-toluenesulfonate, methylsulfate, methanesulfonate, tetrafluoroborate,and perchlorate. When R⁹ represents an acyl, the disulfone reactant isessentially a vinyl ester disulfone; however, for purposes ofsimplicity, the term "vinyl ether disulfone" is used herein to includevinyl ester disulfones.

When the disulfone reactant is an enamine disulfone, a PDFM may beformed according to reactions (iia or iib): ##STR13## where R¹, R²,R_(f) ¹, R_(f) ², R⁵, R⁸, R⁹, Ar, Ar', X, Y, X', Y', W, A.sup.θ, h, h',m, m', n, and p are as defined above.

When the disulfone reactant is an alkenyl disulfone having a methyl ormethylene group, a PDFM may be formed according to reactions (iiia) and(iiib): ##STR14## where R¹, R², R_(f) ¹, R_(f) ², R⁷, R⁸, R⁹, Ar, X, Y,k, m, n, and p are as described above.

In general, the above reactions (ia-iiib) will occur in the liquid phaseat room temperature using a solvent that is capable of dissolving thereactants and is kinetically inert to them. Representative classes ofsuch solvents include alkanes, such as halo- and polyhaloalkanes,aromatic hydrocarbons such as mono and poly- substituted aromaticcompounds, acids, anhydrides, esters, and alcohols. Examples of suchsolvents include hexane, toluene, xylenes, chloroform, chlorobenzene,o-dichlorobenzene, ethyl acetate, acetic acid, acetic anhydride, andethanol. Although the reactions proceed at room temperature, it is oftenadvantageous and usually preferred to heat the reaction mixture to theboiling point of the solvent and to monitor the course of the reactionby thin layer chromatography (TLC). It is also possible in somesituations to use a solvent that dissolves the starting materials butdoes not dissolve the final product. When such a solvent is used, thePDFM product precipitates during the reaction or upon cooling thereaction mixture. The product may then be isolated by filtration.Otherwise, (when the product is not insoluble in the solvent) theproduct may be isolated by cooling, removing solvent in vacuo, andrecrystallizing the residue from another solvent.

The disulfone reactants used to form PDFMs may be prepared as follows.The vinyl ether disulfone may be prepared according to reactions (iva)and (ivb) provided below, the enamine disulfone may be prepared asdescribed in U.S. Pat. No. 3,932,526, and the alkenyl disulfone may beprepared according to exemplary reaction (v) provided below.

A vinyl ether disulfone may be formed by reacting a bis(diacetal) suchas malonaldehyde bis-(dimethyl acetal) (preferably named 1,1,3,3,tetramethoxypropane) or an orthoester such as triethyl orthoformate(Aldrich Chemical Co., Milwaukee, Wis.) with a methane disulfone(prepared as described in R. J. Koshar and R. A. Mitsch, J. Org. Chem.1973 38, 3358-63 and U.S. Pat. No. 3,932,526) in an organic solvent suchas acid anhydride, preferably acetic anhydride. These reactions areillustrated as follows: ##STR15## where R¹, R², R_(f) ¹, R_(f) ², R⁸,R⁹, are as provided above. Reactions (iv) and (v) may occur at roomtemperature or at elevated temperatures. Elevated temperatures arepreferred because there is a significant increase in the rate ofreaction. In general, the reaction will be substantially complete atabout 1 to 4 hours at temperatures above 50° C. Preferred reactiontemperatures are at from 50° to 70° C. At room temperature, the vinylether disulfone is formed in about 20 to 50 hours. This reaction appearsto go to completion, and therefore it is often beneficial to use thevinyl ether disulfone in situ to prepare a PDFM. Alternatively, ifdesired, the vinyl ether disulfone may be isolated by vacuumdistillation before it is reacted with a molecule carrying anelectron-donating group to form a PDFM.

When the vinyl ether disulfone is used in situ, the generation of vinylether disulfone is followed by cooling the mixture, adding an activatedaromatic compound, an activated heterocyclic compound, dye base, or dyeolefin and reacting the vinyl ether disulfone with the activatedaromatic, activated heterocyclic compound, dye base, or dye olefin for afew minutes to 1-2 hours at from about room temperature to about 70° C.to form a PDFM. Some PDFMs have limited solubility in acid anhydridessuch as acetic anhydride and in acetic acid and therefore willprecipitate during the reaction. In this instance, the PDFMs can then bepurified by filtration and washing or recrystallization using methanolor a methanol/water mixture. The reaction can be monitored by TLC ifdesired. When the PDFMs do not precipitate upon formation, they may beisolated by precipitation using aqueous methanol, or by solvent removal,and purified by recrystallization.

It is preferred to add the activated aromatic, dye base, dye olefin, orheterocyclic compound after the vinyl ether disulfone is formed. If allof the reagents are simply mixed together and heated, a low yield ofPDFMs will usually result.

An alkenyl disulfone may be formed, for example, by reacting an aldehydewith a methane disulfone as shown in reaction (v): ##STR16## where R_(f)¹ and R_(f) ² are as provided above.

This reaction may be carried out in solution using a solvent that iscapable of dissolving the reactants and is kinetically inert to them.Representative classes of such solvents may include those that areprovided above as being suitable in the reactions for forming PDFMs.Examples of such solvents are also provided above. The reactions willoccur slowly at room temperature, but it is often preferred to heat thereaction to the boiling point of the solvent, and to remove the water asit is formed using, for example, a Dean-Stark trap. This reactionappears to go to completion. It therefore may be beneficial to use thealkenyl disulfone in situ to prepare PDFMs.

Representative examples of vinyl ether disulfones that may be used toprepare PDFMs include but are not limited to: CH₃ O--CH═C(SO₂ CF₃)₂ ;CH₃ O--CH═CH--CH═C(SO₂ CF₃)₂ ; CH₃ O--CH═C(SO₂ F)₂ ; CH₃O--CH═CH--CH═C(SO₂ F)₂ ; CH₃ O--CH═C(SO₂ C₈ F₁₇)₂ ; CH₃O--CH═CH--CH═C(SO₂ C₈ F₁₇)₂ ; CH₃ O--CH═C(SO₂ CF₃)(SO₂ C₈ F₁₇); CH₃O--CH═CH--CH═C(SO₂ CF₃)(SO₂ C₈ F₁₆); (CH₃ O)(CH₃)C═C(SO₂ CF₃)₂ ; and C₂H₅ O--CH═C(SO₂ CF₃)₂.

Representative examples of enamine disulfones that may be used toprepare PDFMs include but are not limited to: (CH₃)₂ N--CH═C(SO₂ CF₃)₂ ;(CH₃)₂ N--CH═CH--CH═(SO₂ CF₃)₂ ; (CH₂)₄ N--CH═C(SO₂ CF₃)₂ ; and O(CH₂CH₂)₂ N--CH═CH--CH═C(SO₂ CF₃)₂.

Representative examples of alkenyl disulfones that may be used toprepare PDFMs include but are not limited to: CH₃ --CH═C(SO₂ CF₃)₂ ; CH₃--CH═CH--CH═C(SO₂ CF₃)₂ ; CH₃ --CH═C(SO₂ C₈ F₁₇)₂ ; CH₃--CH═CH--CH═C(SO₂ C₈ F₁₇)₂ ; CH₃ --CH═C(SO₂ F)₂ ; CH₃ --CH═CH--CH═C(SO₂F)₂ ; CH₃ --CH═C(SO₂ CF₃)(SO₂ C₈ F₁₇); and CH₃ --CH═CH--CH═C(SO₂CF₃)(SO₂ C₈ F₁₇).

Representative examples of activated aromatic compounds that may be usedto prepare PDFMs by reaction with vinyl ether disulfones include but arenot limited to: N,N-dimethylaniline; N,N-diethylaniline; N,N-dipropylaniline; N-phenyl-morpholine; julolidine; N,N-dimethyl-1-naphthylamine;N,N-diethyl-m-phenetidine; N,N-dimethyl-2,5-dimethoxyaniline; andN,N-dibutylaniline.

Representative examples of activated heterocycles that may be used toprepare PDFMs by reaction with vinyl ether disulfones include but arenot limited to: N-methylindole; N-ethyl-2-phenylindole; and1-p-anisyl-2,5-dimethylpyrrole.

Representative examples of dye bases and quaternary ammonium precursorsof dye bases that may be used to prepare PDFMs by reaction with vinylether disulfones or enamine disulfones include but are not limited to:N-methyl-quinaldinium methylsulfate; N-methyllepidiniump-toluenesulfonate; N-ethyl-2-methylbenzothiazolinium iodide,1,3,3-trimethyl-2-methyleneindolenine; and1,3-diethyl-2-methylimidazo-[4,5b]quinoxalinium p-toluenesulfonate.

Representative examples of dye olefins that be used to prepare PDFMs byreaction with vinyl ether disulfones or enamine disulfones include butare not limited to: 1,1-bis-(4'-N,N-dimethylaminophenyl)ethylene;1,1-bis-(4'-N,N-diethylaminophenyl)ethylene;1-phenyl-1-(4'-N,N-diethylaminophenyl)ethylene (Chem. Abst. Serv. No.115655-10-2, hereinafter cited as "CAS"); and1-(4'-ethoxyphenyl)-1-(4''-N,N-dimethyl-aminophenyl)ethylene (CAS113915-69-8).

Examples of aldehydes that can be used to prepare PDFMs by reaction withalkenyl disulfones include but are not limited to: benzaldehyde;4-methoxybenzaldehyde; mesitaldehyde; 2,3-dimethoxy-5-bromobenzaldehyde;2,5-dimethoxybenzaldehyde; 2-isopropoxybenzaldehyde;2,4,5-trimethoxybenzaldehyde; 4-methoxycinnamaldehyde;4-pentyloxybenzaldehyde; 3-methyl-4-benzyloxybenzaldehyde;4-(methoxymethyl)benzaldehyde; 1-naphthaldehyde; 2-naphthaldehyde;9-anthraldehyde; tolualdehyde; 2-furaldehyde;thiophene-2-carboxaldehyde; and pyrrole-2-carboxaldehyde.

Representative examples of acetals that may be used to prepare PDFMs byreaction with an alkenyl disulfone include: 2-furaldehyde diethylacetal; N,N-diethylaminobenzaldehyde diethyl acetal;N,N-dimethylaminobenzaldehyde diethyl acetal; p-methoxybenzaldehydedimethyl acetal; and o-methoxybenzaldehyde diethyl acetal.

Representative examples of diacetals that may be used to prepare vinylether disulfones include: 1,1,3,3-tetramethoxypropane;1,1,3,3,-tetraethoxypropane; and (CH₃ O)₂ CH--CH₂ --CH═CH--CH(OCH₃)₂(CAS 1116-86-5).

Representative examples of orthoesters that may be used to prepare vinylether disulfones include: triethyl orthoacetate; triethyl orthoformate;triethyl orthopropionate; trimethyl orthoacetate; trimethylorthobenzoate; trimethyl orthobutyrate; trimethyl orthoformate;trimethyl orthovalerate; tripropyl orthoformate; and diethylphenylorthoformate.

Representative examples of aldehydes that may be used to prepare thealkenyl disulfone molecules include but are not limited to:crotonaldehyde; acetaldehyde; propionaldehyde; butyraldehyde; andheptaldehyde. Other useful aldehydes can be found in Organic Reactions,v. 15, Chapter 2, (1967) A. C. Cope ed., New York, the disclosure ofwhich is incorporated here by reference. The aldehydes selected shouldhave at least two active hydrogen atoms.

Representative examples of PDFMs that may be formed by theabove-described process of this invention are shown in Table 1. Some ofthese PDFMs may be formed by the prior art methods disclosed in U.S.Pat. Nos. 3,932,526, 3933,914, 3,984,357, 4,018,810, 4,069,233,4,156,696, and 4,357,405. Whether prepared by the new method of thisinvention or prior art methods, all of the PDFMs appear to be useful forgenerating NLO responses.

New PDFMs of this invention may be represented by Formula I, where n,R¹, R², and Z are as defined above, and R_(f) ¹ and R_(f) ² takentogether in conjunction with the disulfone group form a 5, 6, or7-membered ring containing two, three, or four carbon atoms that arefluorinated, preferably highly fluorinated, more preferablyperfluorinated.

New PDFMs of this invention also include compounds of the Formula I,where n, R¹, R², and are as defined above, and R_(f) ¹ and R_(f) ²independently represent fluorine, a saturated fluorinated alkyl groupcontaining 1 to 10 carbon atoms, or taken together with the disulfonegroup form a 5, 6, or 7-membered ring containing 2, 3, or 4 carbonatoms, respectively, which are fluorinated, with the provisos that (i)at least one of R_(f) ¹ and R_(f) ² is fluorine, and (ii) n is 1 or 2when Z is a group of the Formula II ##STR17## and Y is NR³ R⁴, where Ar,X, Y R³, R⁴, k, and m are as defined above.

Other new PDFMs are the vinyl ether disulfone molecules, which may berepresented by the Formula VII: ##STR18## where R¹, R², R⁸, and R⁹, areas defined above, n is 0, 1, or 2, and R_(f) ¹ and R_(f) ² hereindependently represent fluorine, a saturated fluorinated alkyl radicalcontaining 1 to 10 carbon atoms, or taken together in conjunction withthe disulfone group form a 5, 6, or 7-membered ring containing 2, 3, or4 carbon atoms, respectively, which are fluorinated.

Additional new PDFMs may be represented by the Formula VIII: ##STR19##where R_(f) ¹ and R_(f) ² here independently represent fluorine, asaturated fluorinated alkyl radical containing 1 to 10 carbon atoms, ortaken together in conjunction with the disulfone group form a 5, 6, or7-membered ring containing 2, 3, or 4 carbon atoms, respectively, whichare fluorinated, and R¹⁰ is selected from the group consisting of:##STR20## where n is 0, 1, or 2 and R⁵ is as defined above.

Further new PDFMs are represented by the formula ##STR21## where n is 1or 2 and R⁵ is as defined above.

PDFMs 1-35 illustrated below in Table 1 were prepared in the followingExamples 1-35, respectively. In Examples 1-35 the melting points weredetermined for some of the compounds. Where those melting points weredetermined, those values are shown in Table 1. If the melting point wasnot determined, "n/d" is provided in Table 1. If the compound decomposedat the melting point, "dec." indicates this.

                                      TABLE 1                                     __________________________________________________________________________                                            Melting                               Compound No.                                                                          Structure                       Point (°C.)                    __________________________________________________________________________             ##STR22##                      205-207                                        ##STR23##                      161-165                                        ##STR24##                      154-157                                        ##STR25##                      134-137                                        ##STR26##                      143-147                                        ##STR27##                      156-157                                        ##STR28##                      138-143                                        ##STR29##                      138-148                                        ##STR30##                      210                                   10.                                                                                    ##STR31##                      218                                            ##STR32##                      181-183                               12                                                                                     ##STR33##                      260-263                                        ##STR34##                      148-153 (dec.)                                 ##STR35##                      155-159 (dec.)                                 ##STR36##                      171-173 (dec.)                                 ##STR37##                      n/d                                            ##STR38##                      177-179 (dec.)                                 ##STR39##                      255-257                               19a.                                                                                   ##STR40##                      204-206                               19b.                                                                                   ##STR41##                      213.5-214.5                           19c.                                                                                   ##STR42##                      200-201 (dec.)                        20.                                                                                    ##STR43##                      219-221                                        ##STR44##                      158-163                                        ##STR45##                      131-132                                        ##STR46##                      n/d                                            ##STR47##                      145-147 (dec.)                                 ##STR48##                      253-255 (dec.)                                 ##STR49##                      255-256 (dec.)                                 ##STR50##                      198-200                                        ##STR51##                      242-243 (dec.)                                 ##STR52##                      270-271                               30.                                                                                    ##STR53##                      245-247                               31a.                                                                                   ##STR54##                      143-144                               31b.                                                                                   ##STR55##                      104-119                                        ##STR56##                      176-177 (dec.)                        33a.                                                                                   ##STR57##                      n/d                                   33b.                                                                                   ##STR58##                      n/d                                   33c.                                                                                   ##STR59##                      n/d                                   33d.                                                                                   ##STR60##                      n/d                                   33e.                                                                                   ##STR61##                      n/d                                   33f.                                                                                   ##STR62##                      n/d                                   33g.                                                                                   ##STR63##                      n/d                                   33h.                                                                                   ##STR64##                      n/d                                   33j.                                                                                   ##STR65##                      n/d                                            ##STR66##                      n/d                                            ##STR67##                      197-199                               __________________________________________________________________________

Objects and advantages of this invention are further illustrated in thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention.

EXAMPLES

In Examples A-J, starting materials were made, which were subsequentlyused in reactions to form PDFMs. In Examples A, B, C, and F-L, vinylether disulfones were prepared, and in Examples D and E, an alkenyldisulfone was prepared. In Examples 1-35, compounds 1-35 were prepared,respectively, using in many cases the novel method of the presentinvention. The structures assigned to each of the compounds 1-35 weredetermined using one or more of the following methods: IR spectroscopy;NMR spectroscopy; ultraviolet/visible spectroscopy; product massbalance, and elemental analysis. The PDFMs of this invention typicallydisplay solvatochromy.

Example A Preparation of (CH₃ O)--CH═CH--CH═C(SO₂ CF₃)₂

To a 250 ml round-bottomed flask equipped with a magnetic stirrer, icebath, condenser, and nitrogen atmosphere was added 8.21 g (0.05 mole) of1,1,3,3, tetramethoxypropane (CAS 102-52-3) also known as malonaldehydebis(dimethyl acetal). Acetic anhydride (10 g) was added slowly tominimize the resulting exotherm. The solution was cooled in ice, and asolution of 14.00 g (0.05 mol) of bis(trifluoromethylsulfonyl)methane(CAS 428-76-2), in 10 g of acetic anhydride, was added slowly. Uponcompletion of the addition, the cooling bath was removed, and thesolution was allowed to warm to room temperature. A heating mantle wasattached, and the solution was heated at reflux for 2 hr. The amber-redsolution was cooled to room temperature. Each 2.12 g of this solutionassumedly contained 0.0025 moles of the vinyl ether disulfone.

Example B Preparation and Isolation of (C₂ H₅ O)--CH═C(SO₂ CF₃)₂

Bis(trifluoromethylsulfonyl)methane (28.03 g, 0.10 mol) and 25 g (0.26mol) of acetic anhydride were placed in a 100 ml round-bottomed flaskequipped with a condenser and magnetic stirrer. Stirring was begun, thereactants dissolved, and the solution was cooled in an ice bath andstirred for 10 minutes. Triethylorthoformate, CAS 122-51-0, (14.8 g,0.10 mol) was slowly added over 5 minutes. The ice bath was replacedwith a cold water bath to slowly raise the temperature and moderate theexotherm. After 15 minutes, the water bath was removed and theyellow-orange solution was allowed to stir at room temperature for 1hour. A heating mantle was attached, and the reaction mixture was heatedat reflux for 2 hours. The solution was cooled to room temperature, andthe solvent was removed at reduced pressure of afford a dark viscousoil. The crude material was isolated by vacuum distillation (bp110°-117° C. at 1 mm) to afford 13.26 g (39%) of the vinyl etherdisulfone.

Example C Preparation and Isolation of (CH₃ O)--CH═CH--CH═C(SO₂ CF₃)₂

Bis(trifluoromethylsulfonyl)methane (28.01 g, 0.10 mol) and 20 g aceticanhydride were added to a 250 ml round-bottomed flask equipped withmagnetic stirrer, ice bath, condenser, and nitrogen atmosphere. Stirringwas begun, and upon dissolution of thebis(trifluoromethylsulfonyl)methane, the solution was cooled in an icebath. A solution of 16.42 g (0.01 mol) of 1,1,3,3-tetramethoxypropane in20 g of acetic anhydride was added in 5 g portions over 0.5 hour tominimize the exotherm. The solution turned orange-brown. Upon completionof the addition, the cooling bath was removed, and the solution warmedto room temperature. A heating mantle was attached, and the solution washeated at reflux for 2 hours. The dark amber-red solution was cooled toroom temperature, and solvent was removed at reduced pressure to afforda dark viscous oil. The crude material was isolated by vacuumdistillation (bp 130° C. at 0.3 mm); 25.51 g (73%) of the vinyl etherdisulfone was produced.

Example D Preparation of a Reaction Product Containing CH₃--CH═CH--CH═C(SO₂ CF₃)₂

An alkenyl disulfone was prepared by placing 50 ml of toluene, 1.00 g of85% crotonaldehyde (0.85 g, 0.01 mol (CAS 123-73-9)), 2.80 g (0.01 mole)of bis(trifluoromethylsulfonyl)methane, and about 1 g of anhydroussodium sulfate (as a drying agent) in a 100 ml round-bottomed flask,equipped with magnetic stirrer, condenser, heating mantle, nitrogenatmosphere, and Dean-Stark trap. Stirring was begun, and the mixture washeated at reflux for 4 hr and was stirred overnight, to form the alkenyldisulfone, CH₃ --CH═CH--CH═C(SO₂ CF₃)₂, CAS 58510-89-7.

Example E Preparation of a Reaction Product Containing CH₃--CH═CH--CH═C(SO₂ CF₃)₂

The alkenyl disulfone CH₃ --CH═CH--CH═C(SO₂ CF₃)₂ was prepared by themethod of Example D, except 100 ml of mixed hexanes were used in lieu of50 ml of toluene, and no drying agent was employed. The reactants wereplaced in a 250 ml round bottomed flask equipped as described in ExampleD, stirring was begun, and the mixture was heated at reflux overnight.Water was removed by a Dean trap, and the alkenyl disulfone was formed.

Example F Preparation of Reagent F and Analysis by Formation of Compound7

To prepare PDFMs in which a trimethine group is desired to be introducedbetween the disulfone group and the ring of an aromatic tertiary amine,the olefinic group of a dye base or dye olefin, or the ring of anactivated heterocyclic compound, it is convenient to prepare and use adisulfone-containing reagent containing an active species CH₃O--CH═CH--CH═C(SO₂ CF₃)₂. Such a material (Reagent F) has been produced,for example, using the following procedure.

In a 125 ml Erlenmeyer flask equipped with air condenser, the followingwere mixed: 14.00 g (0.05 mole) bis(trifluoromethanesulfonyl)methane;8.20 g (0.05 mole) 1,1,3,3,-tetramethoxypropane; and 20.4 g (0.20 mole)acetic anhydride. An exothermic reaction occurred which was controlledby means of a water bath. The resultant 42.6 g reaction mixture was"aged" for 24 hours at approximately 25° C. After aging, the reagentbecame dark amber-brown in color. Alternatively, aging can beaccelerated by maintaining the mixture in a closed vessel (to preventloss of methyl acetate formed as a by-product) at 60° C. for one hour,or at 90° C. for 20 minutes; or one might utilize an open vessel andpermit loss of methyl acetate, provided appropriate correction were madein the weight of any aliquot portions used in subsequent reactions.

The quality of Reagent F was tested by placing a 4.26 g (10%) aliquot ofthe reagent in a stoppered 8 ml vial with 0.61 g of dimethylaniline, andmixing Reagent F and dimethylaniline by vigorous shaking. After at leastten minutes, and optionally after warming to 60° C., thepartially-crystallized product was worked up by dilution, filtration,and washing the retained crystalline product (a total of 100 ml ofisopropanol was used for this purpose). The dried product, compound 7,weighed approximately 1.71 g (80% yield based on the disulfone reagent)and had a melting point of 207°-209° C.

Variations in the above reaction conditions have not been found to besignificantly beneficial to yield and/or purity of the product. Thus, ina variation termed F-1, a freshly-made golden-yellow reagent was "aged"at about 25° C. for two minutes, and the product weighed 0.64 g (30%yield). In other variations termed F-2 and F-3, after aging the reagentat approximately 25° C. for 1 hour and for 4 hours, 61% and 68% yieldswere obtained respectively. In a variation F-4, a 71% yield was obtainedafter aging the reagent at 60° C. for 20 minutes. In an equilibriumreaction, an increase above the stoichiometric amount of an equilibratedreagent would be expected to increase the yield. In a variation F-5, a25% excess of acetic anhydride was added and the yield was 75%. In avariation F-6, a 25% excess of 1,1,3,3,-tetramethoxypropane was added tothe reaction mixture, and the yield was 78%. In a variation F-7, inwhich both reactants were present at 25% excess, the yield was 84%. Thisimprovement is considered to be just outside the limits of error (±2%)of the test method.

Example G Preparation of Reagent G and Analysis by Formation of Compound9

When a one-carbon methine is desired for use in preparing PDFMs, it canbe made as described in Example F using the following reactants in thefollowing amounts: 7.41 g (0.05 mole) of triethyl orthoformate (CAS122-51-0); 14.00 g (0.05 mole) of bis(trifluoromethylsulfonyl)methane;and 15.3 g (0.15 mole) of acetic anhydride. After aging at 25° C. forabout 24 hours, a 3.67 g aliquot (0.005 equivalents) of Reagent G isreacted in a stoppered 8 ml vial with 1.33 g (0.005 mole) of1,1-bis(p-dimethylaminophenyl)ethylene (CAS 7478-69-5) 1 hr at 60° C.Reagent G contains the active species C₂ H₅)--CH═C(SO₂ CF₃)₂. Thepartly-crystalline mixture is diluted with 50 to 100 g of isopropanol,heated on the steam bath to dissolve the crystals, cooled to below roomtemperature to effect recrystallization, filtered, washed, and dried. Atleast 2.13 g of compound 9 (78% yield based on the disulfone), isrecovered if Reagent G has been properly aged before use.

Example H Preparation of Reagent H Containing (C₂ C₅ O)--CH═C(SO₂ CF₃)₂

Triethylorthoformate (7.41 g, 0.005 mol) and 31 g of acetic anhydridewere placed in a 100 ml round-bottomed flask equipped with a condenserand magnetic stirrer. Stirring was begun, and upon the dissolving of thereactants, the solution was cooled in an ice bath, and stirred for 10minutes. Bis(trifluoromethylsulfonyl)methane (14.03 g, 0.005 mol) wasslowly added to minimize the exotherm. The ice bath was replaced with acold water bath, and the reaction mixture was allowed to slowly warm toroom temperature. After 15 minutes, the water bath was removed, replacedwith a heating mantle, and the yellow-orange solution was heated at 65°C. for 1 hour. The solution was cooled to room temperature. Each 2.62 gof this solution was calculated to contain 0.0025 mol of the vinyl etherdisulfone adduct.

Example J Preparation of Reagent J Containing CH₃ O--CH═CH--CH═C(SO₂ C₈F₁₇)₂

1,1,3,3-Tetramethoxypropane, 0.18 g (0.0011 mole), 0.51 g (0.005 mole)of acetic anhydride, and 0.98 g (0.001 mole) of (C₈ F₁₇ SO₂)₂ CH₂ (CAS29214-34-4) were placed in a stoppered 8 ml vial and heated on the steambath to 95°-100° C. for one-half hour. The initially golden-yellow pastymix became a clear, reddish-amber-brown solution, designated Reagent J.

Example K Preparation of Reagent K Containing CH₃ O--CH═CH--CH═C(SO₂CF₃)(SO₂ C₈ F₁₇)

In a stoppered 8 ml vial 0.37 g (0.0022 mole) of1,1,3,3,-tetramethoxypropane and 0.82 g (0.008 mole) of acetic anhydridewas added to 1.26 g (0.002 mole) of CF₃ SO₂ CH₂ SO₂ C₈ F₁₇ (CAS30416-80-9). The mixture was heated on a steam bath to 90°-100 ° C. for3/4 hour. An amber-brown solution (Reagent K) was formed.

Example L Preparation of Reagent L Containing CH₃ O--CH═CH--CH═C(SO₂ F)₂

Reagent L was prepared by the process of Example K, except 0.36 g (0.002mole) of CH₂ (SO₂ F)₂, CAS 42148-23-2, was substituted for the CF₃ SO₂CH₂ SO₂ C₈ F₁₇. An amber-brown solution of Reagent L was obtained, andremained in solution on cooling to room temperature.

Example 1

Bis(trifluoromethylsulfonyl)methane (3.00 g, 0.011 mol) and aceticanhydride (25 ml) were placed in a 250 ml round-bottomed flask and werestirred magnetically to obtain a solution. The solution was cooled in anice bath, and a solution of 1.60 g (0.01 mol)1,1,3,3,-tetramethoxypropane in 25 ml of acetic anhydride was slowlyadded. Upon completion of the addition, the cooling bath was removed andreplaced by a heating mantle. The solution was then heated at 70° C. for2 hr, was then cooled to room temperature, and a solution of 1.21 g(0.01 tool ) of N,N-dimethylaniline (CAS 121-69-7) in 5 ml of aceticanhydride was added dropwise. A heating mantle was attached, and thissolution was heated at 70° C. for 2 hours. As the reaction progressed,the solution became deep magenta. The solution was allowed to cool, 125ml of isopropyl alcohol was added slowly, and the solution was stirredovernight. Filtration, followed by washing with methanol and drying,afforded 2.70 g (62%) of compound 1. Its spectrum in 1,2-dichloroethane(used for all spectra unless otherwise stated) showed maximal absorptionλmax at 544 nm, with half-maximal absorption points λ1/2 at 516 and 565nm.

Example 2

An acetal reactant was prepared in a manner similar to the reactiondescribed in J. Klein & E. D. Bergmann, J. Amer. Chem. Soc. 1957, 79,3452-54. This was accomplished by adding 1.49 g (0.01 mol) ofp-N,N-dimethylamino-benzaldehyde (CAS 100-10-7), 100 ml of toluene, 1.75g (0.012 mol) of triethyl orthoformate, and a few milligrams ofp-toluenesulfonic acid to a 250 ml round-bottomed flask equipped withmagnetic stirrer, condenser, heating mantle, and dry nitrogenatmosphere. Stirring and heating were begun, and the solution was heatedat reflux overnight to form p-dimethylaminobenzaldehydebis(diethylacetal).

The solution of Example D containing the alkenyl disulfone CH₃--CH═CH--CH═C(SO₂ CF₃)₂ was added to the acetal solution, and animmediate green solution resulted. The resultant solution was heated atreflux, and the reaction was monitored by thin-layer chromatography(TLC).

Upon cooling, the reaction mixture was filtered and diluted with anequal amount of hexanes to crystallize the resulting PDFM. Filtrationand drying afforded 0.76 g (16%) of compound 2 as green needles. Thiscompound's spectrum had λmax at 634 nm and λ1/2 at 596 and 666 nm.

Example 3

Bis(trifluoromethylsulfonyl)methane (2.80 g, 0.010 mol) and 35 ml oftoluene were placed in a 100 ml round-bottomed flask equipped withmagnetic stirrer, condenser, and nitrogen atmosphere. Upon dissolutionof the bis(trifluoromethylsulfonyl)methane, a solution of 1.48 g (0.01mol) of triethyl orthoformate in 5 ml of toluene was added to theround-bottomed flask. Cooling in an ice bath was followed by adding 3.36g (0.033 mol) of acetic anhydride in 5 ml of toluene. The ice bath wasremoved and replaced by a heating mantle. The solution was heated at50°-70° C. for 3 hr, was then cooled in an ice bath, and a solution of1.49 g (0.010 mol) of N,N-diethylaniline (CAS 91-66-7) in 5 ml oftoluene was added dropwise. A heating mantle was attached, and thesolution was heated at 50°-70° C. for 3 hr. As the reaction progressed,the solution became deep yellow. The solution was allowed to cool, and200 ml of isopropyl alcohol was slowly added. Upon further cooling, afine yellow precipitate separated out from the solution. Filtration,followed by drying, afforded 2.3 g (54%) of compound 3. This compound'sspectrum showed λmax at 455 nm and λ1/2 at 427 and 470 nm.

Example 4

A 2.12 g aliquot of the vinyl ether disulfone solution of Example A,calculated to contain 0.871 g (0.0025 mol) of (CH₃ O)--CH═CH--CH═C(SO₂CF₃)₂, was placed into a small reaction flask, followed by the additionof 0.37 g (0.0025 mol) of N,N-diethylaniline. A reaction occurred, andthe product was isolated by pouring the mixture into a 75/25 (by volume)mixture of methanol and water to precipitate the product, compound 4.This compound's spectrum showed λmax at 549 nm and λ1/2 at 522 and 569nm.

Example 5

A 2.12 aliquot of the vinyl ether disulfone solution of Example A,calculated to contain 0.871 g (0.0025 mol) of (CH₃ O)--CH═CH--CH═C(SO₂CF₃)₂, was placed in a small reaction flask, followed by the addition of0.44 g (0.0025 mol) of N,N-di-n-propylaniline (CAS 2217-07-4). Areaction occurred, and the product was isolated by pouring the mixtureinto a 75/25 (by volume) mixture of methanol and water to precipitatethe product, compound 5. This compound's spectrum showed λmax at 552 nmand λ1/2 at 524 and 572 nm.

Example 6

Compound 6 was prepared as described in Example 1, except that thefollowing were used: 7.00 g (0.025 mol) ofbis(trifluoromethylsulfonyl)methane; 4.10 g (0.025 mol) of1,1,3,3,-tetramethoxypropane; 4.06 g (0.025 mol) of N-phenylmorpholine(CAS 92-53-5); and 25 ml of acetic anhydride. Yield was 2.0 g (17%) ofcompound 6. This compound's spectrum had λmax at 538 nm and λ1/2 at 504and 564 nm.

Example 7

Compound 7 was prepared as described in Example 1, except thatbis(trifluoromethylsulfonyl)methane, 1,1,3,3,-tetramethoxypropane,julolidine (CAS 479-59-4), and acetic anhydride were used. Compound 7was formed having λmax at 571 nm and λ1/2 at 539 and 590 nm.

Example 8

An acetal reactant was prepared by adding 1.36 g (0.01 mol) ofp-anisaldehyde (CAS 123-11-5), 100 ml of hexanes, and 1.75 g (0.012 mol)of triethyl orthoformate to a 500 ml round-bottomed flask equipped withmagnetic stirrer, condenser, heating mantle, and nitrogen atmosphere.Stirring and heating were begun, and the solution was heated at refluxovernight to form p-anisaldehyde bis(diethylacetal), CAS 2403-58-9.

The solution of Example E containing the alkenyl disulfone CH₃---CH═CH--CH═C(SO₂ CF₃)₂ was cooled and was then poured into thesolution containing the acetal reactant. The resulting solution washeated at reflux, the reaction was monitored by TLC, and an orange solidwas formed upon cooling. Filtration and drying afforded 1.00 g (22%) ofcompound 8.

Example 9

Compound 9 was prepared as described in Example 3, except that 2.80 g(0.010 mol) of bis(trifluoromethylsulfonyl)methane, 1.48 g (0.010 mol)of triethyl orthoformate, 2.66 g (0.010 mol) of1,1-bis-(N,N-dimethylaminophenyl)ethylene, (CAS 7478-69-5) and 3.06 g(0.010 mol) of acetic anhydride were used. The product wasrecrystallized three times from isopropanol to afford 4.26 g (78%) ofcompound 9 as dark iridescent green crystals having λmax at 533 nm, andλ1/2 at 504 and 586 nm.

Example 10

Isolated vinyl ether disulfone of Example B of the formula (CH₃O)--CH═CH--CH═C(SO₂ CF₃)₂ (1.74 g, 0.005 mol) and 40 g of absoluteethanol were placed in a 100 ml round-bottomed flask equipped withmagnetic stirrer. A solution of 0.87 g (0.005 mol) of1,3,3-trimethyl-2-methylene-indoline (also known as "Fischer's Base",CAS 118-12-7) was slowly added to the flask. An immediate dark colordeveloped. Stirring was maintained for 2 hr, after which TLC indicatedthe presence of a green and a yellow/orange component. Solvent removalat reduced pressure was followed by column chromatography on silica geland elution with chloroform. The yellow/orange component was elutedfirst. Recrystallization from methanol/ether/pentane afforded 0.80 g(33%) of compound 10.

Example 11

A 2.12 g aliquot of the reaction product of Example A, calculated tocontain 0.871 g (0.0025 mol) of (CH₃ O)--CH═CH--CH═C(SO₂ CF₃)₂ wasplaced in a small reaction flask, followed by the addition of 0.43 g(0.0025 mol) of N,N-dimethyl-1-naphthylamine (CAS 86-56-6). A reactionoccurred, and the product was isolated and purified by recrystallizationfrom methanol. Filtration and drying afforded compound 11 as metallicgreen crystals having λmax at 594 nm, and λ1/2 at 566 and 613 nm.

Example 12

Chloroform (50 ml), 1.68 g (0.005 mol) of an enamine disulfone, (CH₃)₂N--CH═C(SO₂ CF₃)₂, (CAS 58510-91-1) and 2.06 g (0.005 mol) of1,3-diethyl-2-methylimidazo[4,5b]quinoxalinium tosylate (prepared asdescribed in U.S. Pat. No. 3,431,111) were placed in a 100 mlround-bottomed flask equipped with magnetic stirrer and condenser.Stirring was begun, and upon dissolution of the reactants, 0.51 g (0.005mol) of triethylamine was added. An immediate orange colored solutionresulted. After stirring for 3 hr, TLC still indicated the presence ofstarting material. An additional equivalent of triethylamine was added.After an additional 3 hours, starting material remained, and thereaction was heated at reflux overnight. Although the reaction was stillnot complete, the reaction mixture was allowed to cool and wasterminated. The solution was washed twice with 100 ml of water and driedover anhydrous magnesium sulfate for several hours. The drying agent wasremoved by filtration, and solvent was removed at reduced pressure. Theproduct was purified by recrystallization from methanol to afford 1.13 g(43%) of compound 12. This compound's spectrum showed λmax at 433 nm andλ1/2 at 408 and 444 nm.

Example 13

Bis(trifluoromethylsulfonyl)methane (0.28 g, 0.001 mole), 0.16 g (0.001mole) of 1,1,3,3,-tetramethoxypropane, 0.41 g (0.004 mole) of aceticanhydride, and 0.27 g (0.001 mole) of1,1-bis(N,N-dimethylaminophenyl)ethylene were mixed in a stoppered 8 mlvial and shaken. After a few minutes, the mixture solidified to a massof damp crystals, which were worked up in approximately 10 ml of hotisopropanol. Upon cooling, filtration, and drying, 0.46 g of compound 13as dark crystals was obtained in 80% of the theoretical yield. Thecrystals produced blue solutions in organic solvents, and had λmax at641 nm and λ1/2 at 604 and 670 nm.

Example 14

The aged Reagent F of Example F (4.26 g, 0.005 mol equivalents) wasmixed with 0.96 g (0.005 mole) of N,N-diethyl-m-phenetidine (CAS1864-92-2) in a stoppered 8 ml vial and rapidly formed a deep magentaproduct. Workup in approximately 50 ml of methanol:water (3:1 by weight)gave, after filtration and drying, 2.16 g of compound 14 as crystals(86% yield, crude), which after recrystallizing from 100 ml ofethanol:water (3:1 by weight) and drying weighed 1.94 g (77% yield) andhad λmax (in 1,2--C₂ H₄ Cl₂) at 537 nm and λ1/2 at 512 and 555 nm. Indimethylsulfoxide of its molar absorbances were measured to be 21.8 (790nm), 8.89 (830 nm), and 0.00 (1300 and 1560 nm). In 1,2--C₂ H₄ Cl₂ itselectric-field-induced second harmonic (EFISH) generation at 790 nm was11.0 times that of p-nitroaniline (standard), the irradiation being at1580 nm.

Example 15

Compound 15 was prepared by the method of Example 14, except 1.61 g(0.005 mole) of 1,1-bis(p-diethylaminophenyl)ethylene (CAS 6961-56-4)was used instead of the phenetidine compound. A deep blue reaction mixwas produced. Upon workup in methanol, 2.02 g of compound 15 (64% yield)was formed. This compound formed greenish-blue solutions in organicsolvents; in 1,2--C₂ H₄ Cl₂ the λmax was 646 nm, and the λ1/2 were 609and 681 nm.

Example 16

Compound 16 was prepared by the method of Example 14, except that 0.90 g(0.005 mole) of 2,5-dimethoxy-N,N-dimethylaniline (CAS 4034-94-1) wasused instead of the phenetidine compound. A deep purplish product wasformed, which was worked up in isopropanol to form 1.73 g crystals. Thecrystals were recrystallized using aqueous 60 wt.% acetone to give 1.56g (64% yield) of compound 16. The crystals produced purplish solutionsin organic solvents, and had λmax at 568 nm and λ1/2 at 526 and 592 nm.Its EFISH generation at 790 nm was 8.2 times that of p-nitroaniline(irradiation at 1580 nm).

Example 17

Compound 17 was prepared by the method of Example 14, except that 0.65 g(0.005 mole) of N-methylindole (CAS 603-76-9) was used instead of thephenetidine compound. A red-amber liquid product was formed, which uponworkup in a 3:1 (by weight) methanol:water solution formed 1.89 g ofcrystals. Recrystallization from aqueous 50 wt.% acetone gave 1.61 g(74% yield) of compound 17 having λmax at 477 nm and λ1/2 at 455 and 498nm.

Example 18

Reagent G of Example G (3.67 g, 0.005 mol equivalents) was mixed with0.65 g (0.005 mole) of N-methylindole and was heated overnight in astoppered 8 ml vial on a steam bath. Crystals formed, and the productwas worked up by mixing it with 75 g of methanol and 25 g of water. Theprecipitate was filtered off and dried, giving 1.63 g of compound 18 asa red-brown powder (78% yield). Solutions containing compound 18 wereimmensely yellow in color. This compound's spectrum showed λmax at 402nm and λ1/2 at 375 and 423 nm.

Examples 19a, b, c

(a) 4-Dimethylaminobenzaldehyde, 0.60 g (0.0040 mole) was dissolved in15 ml of isopropanol, and to the solution was added 1.00 g (0.0034 mole)of CF₂ (CF₂ SO₂)₂ CH₂, CAS 126136-11-6. The mixture was stirred underreflux for 3 hours, cooled to room temperature, and allowed tocrystallize overnight. The solid product was filtered off, washed withisopropanol, and dried, giving 1.09 g (75% yield) of compound 19a asyellow crystals having λmax at 450 nm.

(b) The procedure of (a) was repeated except the molar scale was reducedby 15% and (CF₂ SO₂)₂ CH₂ was used in lieu of CF₂ (CF₂ SO₂)₂ CH₂. (CF₂SO₂)₂ CH₂ may be obtained in a manner similar to that described for CAS126136-11-6. The recovered product 19b had yellow crystals weighing 0.90g (83% yield) and had λmax at 453 nm, and λ1/2 at 427 and 472 nm.

(c) The procedure of (b) was repeated except for increasing the molarscale by a factor of 2.7 and substituting 4-dimethylaminocinnamaldehyde(CAS 6203-18-5) for 4-dimethylaminobenzaldehyde. The dark crystals ofproduct 19c, 2.90 g (93% yield), had a blue reflex, and a λmax at 537nm, and λ1/2 at 505 and 562 nm.

Example 20

One-half of Reagent L (0.001 molar equivalent) was mixed with 0.12 g(0.001 mole) of dimethylaniline. A reaction occurred at once to give adeep red-magenta mixture which was heated at at 90°-100° C. forapproximately one-half hour. The partly-solid product was diluted withisopropanol, filtered, and washed with isopropanol until the filtratewas no longer amber-colored. The product was then leached with acetoneto extract compound 20 and leave unwanted residues behind. Uponevaporation of acetone from the filtrate, the solid residue, 0.15 g (44%yield) had λmax at 525 nm and λ1/2 at 492 and 550 nm. Its molarabsorbances in the near-infrared region were measured as: 2.32 (790 nm),0.39 (830 nm) and 0.00 (1300 and 1580 nm) in dimethylsulfoxide solution.In 1,2-dichloroethane its EFISH generation at 790 nm was 20.9 times thatof p-nitroaniline.

Example 21

Dimethylaniline (0.14 g, 0.0011 mole) was added to Reagent J of ExampleJ, and the 8 ml vial was shaken vigorously. A deep magenta color formed.After 15 minutes about 7 ml of isopropanol was added to precipitate theproduct. After 10 minutes, the mixture was filtered, and the precipitatewas washed with three 8 ml portions of isopropanol and dried, giving0.64 g (56% yield) of compound 21. Compound 21 displayed enoughsolubility in nonpolar solvents to show solvatochromy. The compound wasvery slightly soluble in pentane, cyclohexane, and hotperfluoro(ethylcyclohexane) to give pale yellow to yellowish-orangesolutions. In a 6:4 perfluoro(ethylcyclohexane):bis(trifluoromethyl)benzene mixture, a light red solution was formed, inbis(trifluoromethyl)benzene a reddish magenta solution was formed, andin warm dimethylsulfoxide a bluish magenta solution was formed. Asaturated solution in 1,2-C₂ H₄ Cl₂ had λmax at 549 nm and λ1/2 at 520and 571 nm.

Example 22

The aged Reagent G of Example G (3.67 g, 0.005 equivalents) was reactedwith 1.11 g (0.005 mole) of 1-p-anisyl-2,5-dimethylpyrrole (CAS5044-27-9) to form an amber-yellow solution from which (in about 5minutes) crystals began to separate. After 2 hours at approximately 40°C., the mix was worked up with 100 ml of 3:1 (by weight) methanol:water.After filtration and drying of the light-yellow product, there wasrecovered 1.71 g (67% yield) of compound 22. Compound 22 formed paleyellow solutions in organic solvents; its λmax in 1,2--C₂ H₄ Cl₂ was at362 nm.

Example 23

Compound 23 was prepared by the method of Example 14, except that 1.11 g(0.005 mole) of 1-p-anisyl-2,5-dimethylpyrrole was used instead of thephenetidine compound. A crystalline product was obtained upon coolingafter 2 hours at approximately 50° C. The product was worked up with 100ml of 3:1 (by weight) methanol:water to give, upon filtration anddrying, 2.20 g of compound 23 (82% yield). This compound formedred-orange solutions in organic solvents.

Example 24

Compound 24 was prepared as described in Example 20, except 0.26 g(0.001 mole) of 1,1-bis(p-dimethylaminophenyl)ethylene was used in lieuof dimethylaniline. Compound 24 was isolated in 77% yield and had λmaxat 630 nm and λ1/2 at 575 and 660 nm. Solutions of it in organicsolvents were intensely blue.

Example 25

Chloroform (50 ml), 1.68 g (0.005 mol) of enamine disulfone (CH₃)₂N--CH═C(SO₂ CF₃)₂, and 1.65 g (0.005 mol) of N-methyl-quinaldiniump-toluenesulfonate (CAS 41626-14-6) were placed in a 100 mlround-bottomed flask equipped with magnetic stirrer and condenser.Stirring was begun and upon dissolution of the reactants, 0.426 g (0.005mol) of piperdine was added. The solution turned yellow, orange, thenorange red, indicating an immediate reaction. After 15 minutes, aprecipitate developed. Stirring for an additional hour was followed bycooling in ice, filtration, and drying to afford 2.07 g (92%) ofcompound 25. This compound's spectrum showed λmax at 436 nm and λ1/2 at401 and 453 nm.

Example 26

The steps of Example 25 were repeated, except 1.65 g (0.005 mol) ofN-methyl-lepidinium p-toluenesulfonate (CAS 42952-26-1) was used in lieuof N-methyl-quinaldinium p-toluenesulfonate. The solution turned yellowindicating an immediate reaction, and a precipitate developed. Stirringfor an additional 1.5 hours was followed by cooling in ice, filtration,and drying to afford 2.05 g (92%) of compound 26.

Example 27

Chloroform (40 ml), 1.68 g (0.005 mol) of enamine disulfone (CH₃)₂N--CH═C(SO₂ CF₃)₂, and 1.53 g (0.005 mol) ofN-ethyl-2-methylbenzothiazolinium iodide (CAS 3119-93-5) were placed ina 100 ml round bottomed flask equipped with magnetic stirrer andcondenser. Stirring was begun and upon dissolution of the reactants,0.426 g (0.005 mol) of piperidine was added. The solution turned orangeindicating an immediate reaction. After one-half hour no precipitate hadformed. The chloroform solution was transferred to a separatory funnel,washed twice with water (2×25 ml), and dried over anhydrous magnesiumsulfate. Filtration, followed by solvent removal at reduced pressureafforded the crude product.

The crude product was purified by dissolving it in about 125 ml ofabsolute ethanol and boiling the solution down to a volume of about 50ml. Upon cooling, the product precipitated as crystals. Filtration anddrying afforded 1.85 g (79%) of compound 27. This compound's spectrumshowed λmax at 411 nm and λ1/2 at 382 and 432 nm.

Example 28

Methanol (20 ml), and 1.65 g (0.005 mol) of N-methyl-quinaldiniump-toluenesulfonate were placed in a 100 ml round-bottomed flask equippedwith magnetic stirrer and condenser. Stirring was begun, and 1.74 g(0.005 mol) of isolated vinyl ether disulfone of Example C of theformula (CH₃ O)--CH═CH--CH═(SO₂ CF₃)₂, was added. Upon dissolution ofthe reactants, 0.51 g (0.005 mol) of triethyl amine was added. Thesolution slowly became orange. A heating bath was attached and thesolution heated at reflux for 3 hours at which time TLC indicated almostcomplete clean reaction. The heating bath was removed and the solutionallowed to stir for 60 hours. A precipitate developed, Stirring for anaddition 60 hours resulted in formation of a precipitate. Cooling inice, filtration, and drying afforded 1.14 g (48%) of compound 28. Thiscompound's spectrum showed λmax at 523 nm and λ1/2 at 477 and 546 nm.

Example 29

Methanol (20 ml), and 1.74 g (0.005 mol) of isolated vinyl etherdisulfone of Example C of the formula (CH₃ O)--CH═CH--CH═C(SO₂ CF₃)₂,were placed in a 100 ml round-bottomed flask equipped with magneticstirrer and condenser. Stirring was begun and upon dissolution of thereactants, 1.65 g (0.005 mol) of N-methyl-lepidinium p-toluenesulfonatewas added. Triethyl amine 0.52 g (0.005 mol) was subsequently added. Theoriginal pale yellow solution turned pale green and then slowly darkenedand became orange. The solution was stirred overnight, a heating bathwas attached, and the solution heated at reflux for 4 hours. The heatingbath was removed, and the reaction mixture was allowed to cool. Coolingin ice, filtration, and drying afforded 0.95 g (40%) of compound 29. Themother liquors were returned to the reaction flask, an additional 0.52 g(0.005 tool) of triethyl amine was added and the mixture was heated atreflux for an additional 18 hours. Filtration afforded an additional0.21 g of product. This compound's spectrum showed λmax at 560 nm andλ1/2 at 507 and 589 nm.

Example 30

Absolute ethanol (30 ml), 1.57 g (0.005 mol) ofN-ethyl-2-methylbenzothiazolinium iodide and 1.74 g (0.005 mol) ofisolated vinyl ether disulfone of Example C of the formula (CH₃O)--CH═CH--CH═C(SO₂ CF₃)₂ were placed in a 100 ml round bottomed flaskequipped with magnetic stirrer and condenser. Stirring was begun and,even though not all of the benzothiazole had dissolved, 0.52 g (0.005mol) of triethyl amine was added. The solution slowly becameorange-yellow, and a precipitate developed as additional benzothiazoleiodide dissolved. Filtration and drying, followed by boiling in methanolfor 20 minutes, cooling, filtering and drying afforded 2.07 g (84%) ofCompound 30. This compound's spectrum showed λmax at 511 nm and λ1/2 at468 and 526 nm.

Examples 31a and b

(a) One-half of Reagent K (0.001 molar equivalent) was reacted with 0.14g (0.0011 mole) of dimethylaniline at 35° C. for one-half hour. To thedeep magenta solution ws added 7 g of isopropanol and the solution wasallowed to crystallize overnight. The solid product, Compound 31a, wasfiltered off, washed with four 7 ml portions of isopropanol, and dried;it weighed 0.52 g (66% yield) and had λmax at 547 nm, and λ1/2 at 520and 568

(b) By the same procedure as (a) but with the substitution of 0.26 g(0.001 mole) of 1,1-bis-(p-dimethylaminophenyl)ethylene for thedimethylaniline, of methanol:water (3:1 by weight) for the isopropanol,and optionally of centrifugation for filtration compound 31b wasobtained in 45% yield and moderate purity. Compound 31b had λmax at 645nm and λ1/2 at 610 and 673 nm. solutions of it in organic solvents wereintensely blue.

Example 32

Provided that an electrophilically-reactive site (commonly para relativeto the activating tertiary amine group) remains accessible,polysubstitution of the benzenoid ring is permissible in a startingmaterial for the dye-forming reaction. Using the procedure of Example14, 0.75 g (0.005 mole) of N,N,3,5-tetramethylaniline (CAS 4913-13-7)and 4.26 g of Reagent F gave Compound 31, 1.54 g (66% yield), havingλmax at 544 nm, and λ1/2 at 518 and 565 nm. Dilute solutions of it inorganic solvents were intensely purplish-magenta in color.

Examples 33a-33j

Following the procedure of Example 32, except that the products were notobtained in crystallinine form; intensely-colored (solution colors inparentheses) reaction products, compounds 33a-33j, were obtained byusing 0.005 mole amounts of the following reactants (a)-(j) respectivelyin lieu of N,N,3,5-tetramethyl-aniline:

(a) N-ethyl-benzo[a]carbazole, CAS 82926-38-3, (violet);

(b) N-ethyl-N-(2-cyanoethyl)aniline, CAS 148-87-8, (red);

(c) N-ethyl-N-(2-cyanoethyl)m-toluidine, CAS 148-69-6, (magenta);

(d) N-methyldiphenylamine, CAS 552-82-9, (magenta);

(e) N,N-dibenzylaniline, CAS 91-73-6, (magenta);

(f) N,N-bis(2-acetoxyethyl)aniline, CAS 19249-34-4, (magenta; λmax=538nm, λ1/2=506 and 562 nm);

(g) N-(2-acetoxyethyl)-N-(2-cyanoethyl)aniline, CAS 22031-33-0,(reddish-magenta; λmax=527 nm, λ1/2=486 and 551 nm);

(h) N,N-bis(2-cyanoethyl)m-toluidine, CAS 18934-20-8, (bluish-red;λmax=520 nm, λ1/2=480 and 543 nm); and

(j) N-phenylpyrrole, CAS 635-90-5, (orange).

The great intensity of the colors resulting from the dissolution (in afew hundred ml of solvent) of a milligram of any of these colored,tarry, dried reaction products attests to the formation in good yield ofthese as-yet-not-crystallized PDFMs.

Example 34

Toluene (5 ml), 0.30 g (0.001 mole) of 4-(bis-p-tolyl)aminobenzaldehyde,CAS 42906-19-4, and 0.28 g (0.001 mole) ofbis(trifluoromethylsulfonyl)methane were placed in a stoppered 8 mlvial, together with 0.60 g B₂ O₃, CAS 1303-86-2, to absorb by-productwater. After a few minutes, the mixture became a strong reddish-ambercolor. After one-half hour at approximately 50° C., a sample waswithdrawn and examined by visible/ultraviolet spectroscopy in1,2-dichloroethane. There was a strong peak at 357 nm and a second oneat 463 nm, about one-fourth as strong. The former was due to thestarting aldehyde and the latter to the product. The reaction mixturewas heated to 95°-100° C. for about 50 hours, at which time the secondpeak had greatly intensified, and the former peak was barely discernibleas a weak shoulder demonstrating completeness of reaction. The productremained soluble in the toluene and was recovered by evaporation todryness followed by washing with heptane to remove by-products and anyunreacted starting material After drying at 100°, the product wasextracted with methyl tertiary-butylether, and on evaporation of thefiltrate to dryness, there was recovered 0.43 g (76% yield) of compound34, a dark-colored solid having λmax at 463 nm and λ1/2 at 432 and 513nm.

Example 35

Toluene (40 ml), 3.35 g (0.01 mol) of enamine disulfone (CH₃)₂N--CH═C(SO₂ CF₃)₂, and 1.73 g (0.01 mol) of1,3,3-trimethyl-2-methylene-indoline were placed in a 100 ml roundbottomed flask equipped with magnetic stirrer and condenser. Stirringwas begun, and the solution heated at reflux for 25 hours. The progressof the reaction was monitored by TLC and proceeded smoothly. Uponcooling, crystals precipitated. One-half of the solvent was removed atreduced pressure and the product redissolved by heating. Upon cooling,crystals again developed. Filtration and drying afforded 3.26 g (70%) ofcompound 35 having λmax at 406 nm and λ1/2 at 376 and 432 nm.

PREPARATION OF NONLINEAR OPTICALLY EFFECTIVE LAYERS Examples 36-50

In each of Examples 36-50, a NLO layer was formed on a substrate from apolymeric composition that contained a PDFM (compounds 1-12, 19c, (CH₃)₂N--C₆ H₆ --C₄ H₄ (SO₂ CF₂)₂ CF₂, and (CH₃)₂ N--C₆ H₆ --C₄ H₄ (SO₂ C₄F₉)₂, respectively) dispersed in a polymer. The prepared layers werethen used to perform second harmonic generation (SHG) of light. InExample 37, electro-optic effects were demonstrated.

Example 36

Compound 1 was dissolved in a polar solvent, and PMMA was added to thesolution. The solution was then spin-coated onto two coplanar chromiumelectrodes on a glass slide separated by a gap of 150 micrometerscreated by conventional photolithographic means. The solvent wasevaporated. The coated slide was then placed on a temperature-controlledcopper block equipped with a hole to let light pass through the gap.Electrical contact was made to the chromium electrodes using stainlesssteel clips. The NLO layer was then heated above T_(g) of the polymer,and a direct current voltage (800-1500V) was applied to the electrodesto align the molecules noncentrosymmetrically. Laser light was thenpassed through the NLO layer. The incident laser light had a frequencyof 1.58 micrometers and was produced by doubling the frequency ofoutputted light from a Nd:YAG laser using a KDP crystal, and passingthat outputted light through a high pressure H₂ Raman cell to obtain thethird Stokes-shifted wavelength. The light was focused through theelectrode gap by means of a cylindrical lens. From the incident light of1.58 micrometers, second-harmonic light of 790 nanometers was thendetected by using a monochromator and a photo-multiplier tube. The layerof NLO material was then cooled while the poling voltage remained, andthe applied field was then removed at room temperature.Noncentrosymmetric alignment of the guest molecules, induced by thepoling electric field, was maintained after the poling voltage wasremoved. This was evidenced by a minor change in the intensity of thesecond harmonic light.

A measure of χ.sup.(2) of the NLO layer was obtained from the ratio ofthe SHG signal from the NLO layer relative to the SHG signal from aquartz crystal. The product of the dipole moment μ and the molecularhyperpolarizability β was then deduced as taught in D. S. Chemla and J.Zyss, "Nonlinear Optical Properties of Organic Molecules and Crystals",vols. I & II,, ch II-7 and II-8 Academic Press, N.Y. (1987). The productof μ and β is shown in Table 2.

Example 37

A NLO layer was prepared as described in Example 35, except compound 2and a copolymer of methylmethacrylate and 2-vinyl-4,4-dimethylazlactone(prepared as described in S. Hellmann et al., J. Poly. Sci. 1984, 22,1179-86 were used in lieu of compound 1 and PMMA, respectively. Secondharmonic light was generated at 790 nm from an incident light of 1.58micrometers. Noncentrosymmetric alignment of the guest molecules wasmaintained after the poling voltage was removed. The NLO layer wastested for its μ,β product; that value is shown in Table 2.

The NLO layer containing compound 2 was tested for utility as anelectro-optic phase shifter. After the poling process was complete andthe poling field was removed at room temperature, the NLO layer wasplaced in the apparatus of FIG. 2 to observe an electro-optic effect.Polarized light at wavelengths of 632.8 nm was passed through theelectrode gap. A modulating voltage was applied to the electrodes toproduce a phase shift of the electric field component parallel to themodulating electric field (relative to the component perpendicular tothe modulating electric field). The phase-shifted light was passedthrough a phase compensator and a polarizer onto a photo-diode detector.When the applied voltage was modulated, the NLO layer's electro-opticeffect produced corresponding changes in the polarization state of thelight passing through the NLO layer.

Examples 38-45, and 47-50

NLO layers were prepared as described in Example 35, except thatcompounds 3-10, 12, 19c, 4-(CH₃)₂ N--C₆ H₄ --(CH)₃ C(SO₂ CF₂)₂ CF₂ and4-(CH₃)₂ N--C₆ H₄ --(CH)₃ C(SO₂ C₄ F₉)₂ were used respectively in lieuof compound 1. The NLO layers demonstrated SHG by emitting light havinga wavelength of 790 nanometers from incident light of 1.58 micrometers.Noncentrosymmetric alignment of the guest molecules was maintained afterthe poling voltage was removed. The product of μ and β were determinedfor each sample; those values are shown below in Table 2.

Example 46

A NLO layer was prepared as described in Example 37, except thatcompound 11 was used as a guest molecule in lieu of compound 2. The NLOlayer demonstrated SHG by emitting light having a wavelength of of 790nm from incident light of 1.58 micrometers. Noncentrosymmetric alignmentof the guest molecules was maintained after the poling voltage wasremoved. The product of μ and β was determined; that value is shown inTable 2. Under these conditions the standard test compound,p-nitroaniline, gives 1-0 for the product of μ and β (in 10²⁸Debye-esu).

                  TABLE 2                                                         ______________________________________                                        Exam-                          μβ × 10.sup.28                   ple  Compound                  Debye-esu                                      ______________________________________                                        35   1                         15                                             36   2                         37                                             37   3                         2.9                                            38   4                         12                                             39   5                         12                                             40   6                         11.5                                           41   7                         7.0                                            42   8                         9.8                                            43   9                         11.7                                           44   10                        7.6                                            45   11                        4.6                                            46   12                        1.2                                            47   19c                       17.7                                           48   *4-(CH.sub.3).sub.2 N--C.sub.6 H.sub.4 --(CH).sub.3 C(SO.sub.2                CF.sub.2).sub.2 CF.sub.2  8.4                                            49   **4-(CH.sub.3).sub.2 N--C.sub.6 H.sub.4 --(CH).sub.3 C(SO.sub.2               C.sub.4 F.sub.9).sub.2    7.0                                            ______________________________________                                         The product of the μ and β values demonstrates that PDFMs possess     a relatively large dipole moment and hyperpolarizability.                     *This compound may be prepared as described in Example 19a by using           4dimethylaminocinnamaldehyde in lieu of 4dimethylaminobenzaldehyde.           **This compound may be prepared as described in Example 21 by using           (C.sub.4 F.sub.9 SO.sub.2).sub.2 CH.sub.2 (CAS 2921437-7) in lieu of          (C.sub.8 F.sub.17 SO.sub.2).sub.2 CH.sub.2.                              

Examples 51-62

In Examples 51, 56, 59, and 61, the light absorption characteristics forPDFMs were examined over the molecule's highest-wavelength peak. InComparative Examples 52-55, 57-58, 60, and 62, the light absorptioncharacteristics for polar-functionalized molecules havingelectron-accepting groups other than a disulfone group (yet with similardonor groups) were examined over the same band of wavelengths. The testswere performed by dissolving the molecules in dichloroethane at 10⁻⁵molar concentrations, and measuring the molecules' light absorptioncharacteristics in a spectrometer.

The molecules tested and the results of the absorption measurements areshown in Table 3. The "half-height-half-bandwidth" Δυ_(1/2) is equal tothe number of wave numbers away from peak absorption and at longerwavelength, where the absorption is 1/2 the peak value. Δυ_(1/10)represents the analogous point at 1/10 of peak absorption.

                                      TABLE 3                                     __________________________________________________________________________                                    Δν.sub.1/2                                                               Δν.sub.1/10                      Example                                                                            Structure                  (× 10.sup.3 cm.sup.-1)                  __________________________________________________________________________          ##STR68##                 0.70                                                                              1.22                                            ##STR69##                 1.46                                                                              2.37                                            ##STR70##                 2.22                                                                              3.69                                            ##STR71##                 1.94                                                                              3.35                                            ##STR72##                 1.83                                                                              2.87                                            ##STR73##                 0.73                                                                              1.41                                            ##STR74##                 1.09                                                                              1.86                                            ##STR75##                 1.01                                                                              1.70                                            ##STR76##                 1.20                                                                              1.98                                      60.                                                                                 ##STR77##                 1.92                                                                              3.08                                      61.*                                                                                ##STR78##                 1.14                                                                              1.98                                            ##STR79##                 1.74                                                                              2.60                                      __________________________________________________________________________     *Compound 61 was made from panisaldehyde (CAS 12311-5) by the method of       U.S. Pat. No. 3,933,914.                                                 

The data shown in Table 3 demonstrate that the PDFMs absorb less lightat long wavelengths when compared to polar molecules having similarelectron-donating groups. The PDFMs are shown to have a narrowerabsorption peak, absorbing less light in and near the infrared region.This is deemed to be a very important property for NLO materialsintended to operate with diode lasers as the light source.

Example 63 Attaching a PDFM to a Polymer

In this example, a polymer was prepared which had a polar moietycomprising a disulfone-functionalized group covalently bonded to thepolymer's sidechains. The prepared polymer (a) had the followingstructure: ##STR80## where x is as defined above. To prepare thispolymer, poly(methacryloyl chloride) (0.21 g, 2 mmol equivalents, fromPolyscience, Inc., Warrington, Pa.) and1,1-bis(trifluoromethanesulfonyl)-2-(2-hydroxy-4-(N,N-diethylamino)phenyl)ethane:##STR81## (0.91 g, 2 mmol prepared as described in U.S. Pat. No.3,933,914, Example 1 by using 2-hydroxy-4-(N,N-diethylamino)benzaldehyde (CAS 17554-90-4) instead of p-dimethylaminocinnamaldehyde)were dissolved in 20 ml of anhydrous 1,2-dichloroethane and warmed to70° C. under dry nitrogen with stirring. Anhydrous pyridine (0.32 g, 4mmol) was added all at once with a syringe. The reaction proceededexothermically. After 4 hours of additional heating, the reaction wascooled, and the product precipitated by adding 200 ml methanol. Theproduct was collected by filtration, and after vacuum drying weighed0.09 g. TLC showed no free PDFMs present. Using absorption measurements,it was determined that x was approximately 0.03.

Preparation and measurement techniques were identical to those used forthe PDFMs dispersed in PMMA. The polymer was spin coated onto a pair ofco-planar chromium electrodes on a fused silica substrate and was poledat 145° C. with a field of 6×10⁴ volts/cm. The polymer successfullygenerated second harmonic light at 790 nm from irradiation by lighthaving a fundamental wavelength of 1580 nm. The signal level wasconsistent with measurements made on Compound 3 (Example 3) dispersed inPMMA. That is, at the same concentration of NLO groups and filmthickness, essentially the same signal level was observed relative tothe SHG signal from a quartz crystal. After poling, the film was cooledto room temperature while maintaining the field. The second harmonicsignal showed virtually no change after the field was removed,indicating stable alignment of the polar moiety in the polymer.

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention. It therefore should be understood that thescope of this invention is not to be limited to illustrative embodimentsset forth herein, but is to be determined by the limitations set forthin the claims and equivalents thereof. It is to be further understoodthat this invention may be suitably practiced in the absence of anyelement that is not disclosed herein.

What is claimed is:
 1. A nonlinear optical composition of matter, whichcomprises: polar disulfone-functionalized molecules incorporated in andaligned noncentrosymmetrically in an optically clear polymericcomposition, wherein the polar disulfone-functionalized molecules are ofthe Formula I ##STR82## where n is 0, 1, or 2; R¹ and R² eachindependently represent hydrogen, an alkyl group of about 1 to 4 carbonatoms, or taken together in conjunction with the catenary carbon atomstherebetween form a 5 or 6-membered carbocyclic or heterocyclic ting,when n is 2, R¹ and R², R¹ and R¹, or R² and R², in conjunction with thecatenary carbon atoms therebetween, may form the 5 or 6-memberedcarbocyclic or heterocyclic ring; R_(f) ¹ and R_(f) ² each independentlyrepresent fluorine, a saturated fluorinated alkyl radical having 1 to 10carbon atoms, or taken together in conjunction with the disulfone groupform a 5, 6, or 7-membered ring containing 2, 3, or 4 carbon atoms,respectively, that are fluorinated; and Z represents an aryl groupsubstituted with an electron donating group, an activated aromaticheterocyclic group, a group derived from a dye base, or a group derivedfrom a dye olefin, wherein;the aryl group substituted with anelectron-donating group is represented by the Formula II ##STR83## whereAr- represents a monovalent aryl group having 6 to 10 ring atoms; Yrepresents an electron-donating substituent group having up to 20 atoms;X represents a monovalent substituent group having 1 to 20 atoms; k is 1or 2; and m is an integer of 0 to 6; the activated heterocyclic aromaticgroup is represented by the Formula III ##STR84## where ##STR85##represents a monovalent heterocyclic aromatic nucleus containing 5 or 6ring atoms: V represents X, or taken together with atoms in theheterocyclic aromatic nucleus represents the necessary atoms required tocomplete a 6-membered aromatic nucleus; E is S, O, or NR⁵, where R⁵represents a substituent containing up to 20 carbon atoms; and g is aninteger of 0 to 4; the group derived from a dye base is represented bythe Formula IV ##STR86## where p is 0, or 1; R⁵ is as defined above; andW represents the non-metallic atoms required to complete a heterocyclicnucleus containing 5 or 6 atoms in the heterocyclic ring; and the groupderived from the dye olefin is represented by the Formula V ##STR87##where Ar, Y, X, and m are as defined above; Ar' independently representsAr; X' and Y' independently represent X and Y, respectively; m'independently represents m; and h and h' independently represents 0, 1,or 2, with the proviso that both h and h' cannot be
 0. 2. The nonlinearoptical composition of claim 1, wherein the electron-donating group hasa σ_(p) value of less than -0.3.
 3. The nonlinear optical composition ofclaim 1, wherein the polar disulfone-functionalized molecules areincorporated in the optically clear polymeric composition by chemicallyreacting the polar disulfone-functionalized molecules with a polymer orwith precursors to a polymeric composition.
 4. The nonlinear opticalcomposition of claim 1, wherein the carbon atoms of R_(f) ¹ and R_(f) ²adjacent and next adjacent to the --SO₂ -- groups are perfluorinated. 5.The nonlinear optical composition of claim 1, wherein R_(f) ¹ and R_(f)² are perfluorinated.
 6. The nonlinear optical composition of claim 1,wherein R_(f) ¹ and R_(f) ² are both CF₃.
 7. The nonlinear opticalcomposition of claim 1, whereinY and Y' are conjugatively locatedrelative to the conjugating group extending between theelectron-donating and electron-withdrawing groups and independently arean amino group of the formula R³ R⁴ N-- or an ether or thio group of theformula R³ O-- or R³ S--, where R³ and R⁴ independently represent amonovalent alkyl of 1 to 12 carbon atoms, cyanoaklyl of 1 to 4 carbonatoms, an aryl, alkaryl, or arylene group having 6 to 10 ring atoms andless than about 15 total carbon atoms, an alkylene, alkyleneoxy,alkylene-tert-amino, or alkylenethio group 1 to 3 carbon atoms, analkyleneacylamino having 1 to 3 ring atoms, an aralkyl group of up toabout 15 total carbon atoms, or R³ and R⁴ taken together in conjunctionwith the nitrogen atom form one or more 5 or 6-membered heterocyclicrings; E is NR⁵, where R⁵ represents a substituent containing up totwenty carbon atoms; and X and X' independently are a halo, asubstituted or unsubstituted aryl group Ar- as defined above, a loweralkyl or a substituted lower alkyl having from 1 to 4 carbon atoms, analkoxy group having from 1 to 4 carbon atoms, a haloalkyl having from 1to 4 carbon atoms, an acyloxy group having from 1 to 4 carbon atoms, anacylamido having from 1 to 10 carbon atoms, saturated cyclics orheterocyclics having from 3 to 10 carbon atoms, an alkylthio grouphaving from 1 to 10 carbon atoms, an aryl or substituted aryl grouphaving 6 to 10 ring atoms, an aralkyl group having from 7 to 15 carbonatoms, an alkenyl having 2 to 15 carbon atoms, or an aralkenyl havingfrom 8 to 15 carbon atoms.